CN112442067A - Phosphorus-nitrogen-containing flame retardant with hydroxyl and preparation method and application thereof - Google Patents
Phosphorus-nitrogen-containing flame retardant with hydroxyl and preparation method and application thereof Download PDFInfo
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/40—Esters thereof
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4075—Esters with hydroxyalkyl compounds
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
- C07F9/24—Esteramides
- C07F9/2404—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/2408—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic of hydroxyalkyl compounds
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
- C07F9/24—Esteramides
- C07F9/2454—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic
- C07F9/247—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic of aromatic amines (N-C aromatic linkage)
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
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- 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
- C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
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- C07F9/6506—Five-membered rings having the nitrogen atoms in positions 1 and 3
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
- C08G18/3889—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus having nitrogen in addition to phosphorus
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
- C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6928—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/30—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen phosphorus-containing groups
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
The invention provides a phosphorus-nitrogen-containing flame retardant with hydroxyl, and a preparation method and application thereof. The molecular chain of the flame retardant provided by the invention contains phosphorus and nitrogen, and the phosphorus and nitrogen can synergistically retard flame, so that the flame retardant effect of the flame retardant provided by the invention can be improved. Meanwhile, the flame retardant with hydroxyl groups provided by the invention can be used as a reaction monomer or a chain extender to participate in the reaction, and finally, the phosphorus and nitrogen containing groups can exist in a reaction system in a chemical bond form, namely, the phosphorus and nitrogen containing flame retardant provided by the invention can realize permanent flame retardance.
Description
Technical Field
The invention belongs to the technical field of flame retardants, and relates to a phosphorus-nitrogen-containing flame retardant with hydroxyl groups, and a preparation method and application thereof.
Background
The flame retardant is a functional auxiliary agent for endowing the flammable polymer with flame retardancy; the flame retardant is divided into an additive flame retardant and a reactive flame retardant according to application modes. The additive flame retardant mainly includes, depending on the composition, inorganic flame retardants, halogen-based flame retardants (organic chlorides and organic bromides), phosphorus-based flame retardants (red phosphorus, phosphoric esters, halogenated phosphoric esters, and the like), nitrogen-based flame retardants, and the like.
The halogen flame retardant generates more smoke and releases irritant and corrosive gases in the combustion process, so that the environment is polluted and the human health is harmed; the european union has banned the use of halogen flame retardants in 2006.
The phosphorus flame retardant is a substitute product of the most important halogen-free flame retardant because the phosphorus flame retardant meets the advantages of no halogenation, low smoke, no use limitation and the like, so that the phosphorus flame retardant becomes one of the important research directions in the flame retardant field at present. The addition amount of the simple organic phosphorus flame retardant is large, and the influence on the mechanical property, the electrical property and the like of the material is large. Nitrogen-containing flame retardants are widely favored because of high efficiency, low toxicity, low smoke, and environmental friendliness. After the phosphorus flame retardant is combined with the nitrogen flame retardant, a more obvious synergistic effect can be generated.
The red phosphorus in the phosphorus flame retardant has the best flame retardant effect and the highest flame retardant efficiency, because the red phosphorus is a complete phosphorus simple substance in theory, the phosphorus content can reach 100 percent, although the phosphorus content is reduced after coating, the phosphorus content is far higher than other phosphorus compounds, and the moisture absorption and the processing thermal stability of the coated red phosphorus are more convenient to store and transport, so the red phosphorus is the most widely used in thermoplastic materials in the phosphorus flame retardant at present. Although the additive flame retardant has the advantage of convenient use, and the phosphorus flame retardant can be matched with the nitrogen flame retardant for use, the additive flame retardant has poor compatibility with resin, and a micromolecule precipitation phenomenon exists along with the passage of time, and part of the additive flame retardant is easy to dissolve in water, so the additive flame retardant cannot realize real environment-friendly flame retardance.
Therefore, there is a need to develop a new reactive flame retardant, which contains phosphorus and nitrogen, and can achieve synergistic flame retardancy and truly realize environment-friendly, safe and flame retardant.
Disclosure of Invention
The invention aims to provide a phosphorus-nitrogen-containing flame retardant with hydroxyl groups, and a preparation method and application thereof. The molecular chain of the flame retardant provided by the invention contains phosphorus and nitrogen, and the phosphorus and nitrogen can synergistically retard flame, so that the flame retardant effect of the flame retardant provided by the invention can be improved. Meanwhile, the flame retardant with hydroxyl groups provided by the invention can be used as a reaction monomer or a chain extender to participate in the reaction, and finally, the phosphorus and nitrogen containing groups can exist in a reaction system in a chemical bond form, namely, the phosphorus and nitrogen containing flame retardant provided by the invention can realize permanent flame retardance.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a phosphorus-nitrogen-containing flame retardant with hydroxyl groups, wherein the phosphorus-nitrogen-containing flame retardant has a structure shown in formula I:
wherein L is1、L2Each independently is preferably a group containing a terminal hydroxyl group.
A is a reactive cyclic group.
Z1、Z2Each independently is preferably a phosphorus-containing group.
M1Selected from linear alkylene, branched alkylene or arylene.
M2Selected from any organic group that satisfies the chemical environment.
Y1、Y2Each independently is preferably an inert group, a sulfur atom, an oxygen atom or-H.
X1Selected from any organylene group that satisfies a chemical environment.
a. b, c, d, f, g and h are independent integers of 0-5, a and b are not 0 at the same time, f and g are not 0 at the same time, g and h are not 0 at the same time, and b + c + h is less than or equal to 5 and a + d + g is less than or equal to 5.
e is an integer from 0 to 100, such as 2, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, and the like.
The phosphorus-containing flame retardant with hydroxyl provided by the invention is phenolic hydroxyl when the hydroxyl is connected with an aromatic group, and the hydroxyl also comprises the phenolic hydroxyl.
Preferably, the first and second electrodes are formed of a metal,Z1、Z2each independently preferably
X2None or selected from any organylene group, R, satisfying the chemical environment1Is methyl or ethyl.
Preferably, X2No or selected from-NH-or C1-C30 linear or branched alkylene.
Preferably, X2No or selected from-NH-or C1-C5 linear or branched alkylene.
Preferably, said M1Selected from the group consisting of C1-C30 linear or branched alkylene, C6-C30 arylene, and C5-C7 heteroarylene, more preferably C1-C5 linear alkylene, C3-C5 branched alkylene, or phenyl, still more preferably C1-C3 linear alkylene, C3 branched alkylene, or phenyl.
The C1-C30 can be C2, C4, C6, C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28 and the like.
The C6-C30 can be C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28 and the like.
The C5-C7 may be C6 or the like.
The C1-C5 linear alkylene group may be methylene, ethylene, propylene, butylene, etc.
The C3-C5 may be C3, C4, C5, etc.
The C1-C3 may be C1, C2, C3, etc.
Preferably, said M2Selected from N, S, C1-C30 straight chain or branched chain alkyl, C6-C30 aryl, C5-C7 heteroaryl,
The C1-C30 can be C2, C4, C6, C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28 and the like.
The C6-C30 can be C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28 and the like.
The C5-C7 may be C6 or the like.
Preferably, Y1、Y2Each independently is preferably-H or ═ O.
Preferably, said X1Selected from N, S, substituted or unsubstituted C1-C30 linear or branched alkylene, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C5-C7 heteroarylene, substituted or unsubstituted C1-C30 alkyleneamine, substituted or unsubstituted C1-C30 alkyleneacyl, substituted or unsubstituted C1-C30 alkyleneester, substituted or unsubstituted C6-C30 alkyleneamine, substituted or unsubstituted C6-C30 aryleneacyl or C6-C30 aryleneester, further preferably substituted or unsubstituted C1-C5 linear or branched alkylene, substituted or unsubstituted C1-C5 alkyleneamine, substituted or unsubstituted C1-C5 alkyleneacyl or substituted or unsubstituted C1-C5 alkyleneester, further preferably-NH-R-, -R '-NH-, -R' -O-, -RV-C (O) -, substituted or unsubstituted C1-C5 linear or branched alkylene, wherein, R, R', R ", RVEach independently is preferably a substituted or unsubstituted C1-C10 straight or branched chain alkylene group.
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. By "stable compound" is meant a compound that can be isolated from a reaction mixture sufficiently robustly to an effective purity and formulated to be effective.
The C1-C30 can be C2, C4, C6, C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28 and the like.
The C6-C30 can be C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28 and the like.
The C5-C7 may be C6 or the like.
The C1-C5 may be C1, C2, C3, C4, C5, etc.
The following description is merely an explanation of structures such as alkyleneamino groups, and R does not particularly denote any meaning.
The alkyleneamino group refers to-R-NH-, wherein R is alkylene.
The alkylene acyl refers to-R-C (O) -, wherein R is alkylene.
The alkylene ester group means-R-COO-wherein R represents an alkylene group.
The arylene amine group means-Ar-NH-, wherein Ar represents an arylene group.
The aryleneacyl group means-Ar-C (O) -, wherein Ar represents an arylene group.
The arylene ester group means-Ar-COO-in which Ar represents an arylene group.
Preferably, said R is2、R3、R4、R5、R6、R7、R8、R9Independently of one another, they are preferably C1-C6 linear or branched alkylene radicals.
The C1-C6 may be C2, C3, C4, C5, etc.
Preferably, n, m, i, k are each independently integers preferably from 0 to 30, such as 1, 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, etc.
Preferably, the phosphorus-nitrogen-containing flame retardant having hydroxyl groups is selected from
The invention does not limit the preparation method of the phosphorus-nitrogen-containing flame retardant with hydroxyl, and any preparation method capable of obtaining the compound of the invention can be adopted, and the preparation method is exemplified as follows:
in a second aspect, the present invention provides a method for preparing a phosphorus-nitrogen-containing flame retardant having a hydroxyl group according to the first aspect, the method comprising the steps of:
the phosphorus-containing flame retardant with hydroxyl is obtained by the addition reaction of a compound containing a-P-H bond and a compound containing an unsaturated bond and/or a cyclic group.
Or, contains-P-L-COH- (A)1)2The hydroxyl of the compound (A) and the available reactive groups of other compounds react to obtain the phosphorus-containing flame retardant with hydroxyl;
wherein L is absent or selected from any organylene group that satisfies a chemical environment.
A1May be H or selected from any organic group that satisfies the chemical environment.
In the present invention, the reactive group carried by the other compound may be a group reactive with a hydroxyl group such as an amine group, a carboxyl group, an ester group, or the like, and may be reacted with dehydration, dealcoholization, or the like.
In a third aspect, the present invention provides a use of the phosphorus-nitrogen containing flame retardant having hydroxyl groups according to the first aspect in the preparation of a polyurethane resin, a phenol resin, a polyester resin, a polyamide resin, an alkyd resin or a silicone rubber resin.
In a fourth aspect, the present invention provides a chain extender comprising the phosphorus-nitrogen-containing flame retardant having hydroxyl groups according to the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) the molecular chain of the flame retardant provided by the invention contains phosphorus and nitrogen, and the phosphorus and nitrogen can synergistically retard flame, so that the flame retardant effect of the flame retardant provided by the invention can be improved. Meanwhile, the flame retardant with hydroxyl groups provided by the invention can be used as a reaction monomer or a chain extender to participate in the reaction, and finally, the phosphorus and nitrogen containing groups can exist in a reaction system in a chemical bond form, namely, the phosphorus and nitrogen containing flame retardant provided by the invention can realize permanent flame retardance.
(2) The phosphorus-nitrogen-containing flame retardant with hydroxyl provided by the invention can be used as a preparation monomer or a chain extender of polyurethane resin, polyester resin, alkyd resin, silicon rubber, polyamide resin and the like.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. 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.
Preparation example 1
A phosphorus-nitrogen-containing flame retardant with hydroxyl has the following structure:
the preparation method comprises the following steps:
1mol of diethanolamine, 1mol of dimethyl hydroxymethyl phosphite, 500mL of ethanol, 0.1mol of sodium hydroxide and 0.1g of DMAP are put into a three-port 2000mL glass reactor with a stirring device, the temperature is raised until the ethanol flows back, the reaction is carried out for 24 hours under stirring, the reaction is washed to be neutral after the reaction is finished, and the phosphorus-nitrogen-containing flame retardant with the structure is obtained after impurity removal.
1H NMR(400MHz,DMSO-d6):δ＝4.26-4.28(t,2H,-OH),3.63-3.66(m,4H,-N-CH2-C 2H-OH),3.47-3.49(d,6H,-P-O-CH3),2.82-2.84(d,2H,-P-C 2H-)2.53-2.55(t,4H,-N-C 2H-CH2-OH).
Preparation example 2
A phosphorus-nitrogen-containing flame retardant with hydroxyl has the following structure:
the preparation method comprises the following steps:
1mol of 2, 2-bis (4-hydroxy-3-aminophenyl) propane, 2.1mol of trimethyl phosphate, 200mL of DMF, 0.1mol of sodium hydroxide and 0.1g of DMAP are put into a three-port 500mL glass reactor with a stirring device, heated until ethanol refluxes, reacted for 24 hours under stirring, washed to be neutral after the reaction is finished, and then the phosphorus-nitrogen-containing flame retardant with the structure is obtained after impurity removal.
1H NMR(400MHz,DMSO-d6):δ＝9.77-9.80(s,2H,-OH),6.51-6.60(dd,6H,ph-H),4.38-4.42(s,2H,-NH-),3.80-3.84(d,12H,-P-O-CH3),1.65-1.72(s,6H,-CH3).
Preparation example 3
A phosphorus-nitrogen-containing flame retardant with hydroxyl has the following structure:
the preparation method comprises the following steps:
1mol of 4- (2-hydroxyethyl amino) phenol, 2.1mol of trimethyl phosphate, 200mL of DMF, 0.1mol of sodium hydroxide and 0.1g of DMAP are added into a three-port 500mL glass reactor with a stirring device, the temperature is increased to ethanol reflux, the mixture reacts for 24 hours under stirring, and after the reaction is finished, the mixture is washed by water to be neutral, and impurities are removed to obtain the phosphorus-nitrogen-containing flame retardant with the structure.
1H NMR(400MHz,DMSO-d6):δ＝9.399.41(s,1H, ph-OH),6.72-6.64(m,2H, ph-H adjacent to-OH), 6.50-6.42(m,2H, ph-H),4.64-4.68(t,1H, -OH),3.76-3.80(d,6H, -P-O-CH)3),3.55-3.60(m,2H,-CH2-OH),3.24-3.27(t,2H,-N-CH2-).
Preparation example 4
A phosphorus-nitrogen-containing flame retardant with hydroxyl has the following structure:
the preparation method comprises the following steps:
adding 1mol of 5- [ (2-hydroxyethyl) -amino ] -2-cresol, 2.1mol of trimethyl phosphate, 200mL of DMF, 0.1mol of sodium hydroxide and 0.1g of DMAP into a three-port 500mL glass reactor with a stirring device, heating until ethanol refluxes, reacting for 24 hours under stirring, washing to be neutral after the reaction is finished, and removing impurities to obtain the phosphorus-nitrogen-containing flame retardant with the structure.
1H NMR (400MHz, DMSO-d 6). delta. delta.7.10-7.13 (s,1H, ph-OH),6.79-6.83(m,1H, ph-H with ph attached to the methyl group), 6.10-6.15(m,1H, ph-H with phenolic hydroxyl para-positioned), 5.78-5.85(m,1H, ph-H),3.76-3.80(d,6H, -P-O-CH)3),3.55-3.60(m,2H,-CH2-OH),3.24-3.27(t,2H,-N-CH2-),2.12-2.16(d,3H,ph-CH3).
Preparation example 5
A phosphorus-nitrogen-containing flame retardant with hydroxyl has the following structure:
the preparation method comprises the following steps:
adding 1mol of dimethyl phosphite, 1mol of paracetamol and 100mL of ethanol into a three-neck flask with a magnetic stirring thermometer, controlling the temperature below 5 ℃ in an ice-water bath under stirring, dropwise adding 2mol of triethylamine, gradually heating and refluxing, continuously reacting for 5 hours, and carrying out reduced pressure distillation to obtain the phosphorus-nitrogen-containing flame retardant with the structure.
1H NMR(400MHz, DMSO-d 6: -delta-9.39-9.41 (s,1H, ph-OH),6.54-6.62(m,2H, ph-H adjacent to-OH), 6.44-6.54(m,2H, ph-H),6.14-6.18(s,1H, -NH-),4.70-4.74(s,1H, -OH),3.76-3.80(d,6H, -P-O-CH)3),1.54-1.60(s,3H,-CH3).
Preparation example 6
A phosphorus-nitrogen-containing flame retardant with hydroxyl has the following structure:
the preparation method comprises the following steps:
adding 1mol of dimethyl phosphite, 1mol of 1- (2-hydroxyethyl) -2-imidazolidinone and 100mL of ethanol into a three-neck flask with a magnetic stirring thermometer, stirring, controlling the temperature to be below 5 ℃ in an ice-water bath, dropwise adding 2mol of triethylamine, gradually heating and refluxing, continuing to react for 10h, and carrying out reduced pressure distillation to obtain the phosphorus-nitrogen-containing flame retardant with the structure.
1H NMR(400MHz,DMSO-d6):δ＝4.95-4.99(s,1H,-C-OH),4.24-4.30(t,1H,-CH2-OH),3.64-3.70(m,2H,-C 2H-OH),3.72-3.78(d,6H,-P-O-C 3H),2.66-2.70(m,2H,-NH-C 2H-CH2-N-),2.55-2.59(t,2H,-C 2H-CH2-OH),2.46-2.54(t,2H,-NH-CH2-C 2H-N-),2.30-2.34(t,1H,-NH-).
The application of the phosphorus-nitrogen-containing flame retardant with hydroxyl groups prepared by the invention in the preparation of polyurethane resin is as follows:
examples 1 to 6
A polyurethane particle is prepared by the following steps:
30 parts by weight of phosphorus-nitrogen-containing flame retardant, 110 parts by weight of isophorone diisocyanate, 55 parts by weight of hydroxyl-terminated polytetrahydrofuran having a molecular weight of 2000, 5 parts by weight of ethylene glycol and 1 part by weight of catalyst were mixed and extruded by a twin-screw extruder to obtain polyurethane particles.
Wherein the flame retardant is the phosphorus-nitrogen-containing flame retardant with hydroxyl provided by preparation examples 1-6 respectively.
Comparative example 1
The phosphorus and nitrogen containing flame retardant is completely replaced by hydroxyl-terminated polytetrahydrofuran with molecular weight of 2000.
Comparative examples 2 to 3
On the basis of comparative example 1, triphenyl phosphate, which is a flame retardant, was added in an amount of 30 parts by weight (comparative example 2) and 75 parts by weight (comparative example 3).
Performance testing
The polyurethane particles provided in examples 1 to 6 and comparative examples 1 to 3 were subjected to a performance test as follows:
(1) combustibility: testing according to UL-94 vertical burning test standard;
(2) tensile strength and elongation: the method is carried out according to the regulation of GB/T528-2009, the test speed (500 +/-50) mm/min and the thickness of a sample are 10 mm;
(3) flame retardant stability: the polyurethane composition was soaked in water for 1 hour and dried to measure its flammability again.
The results of the tests on the examples and comparative examples are shown in Table 1:
TABLE 1
As can be seen from the examples and performance tests, the reactive flame retardant with hydroxyl provided by the invention can participate in the preparation process of polyurethane resin, has stability, and can improve the mechanical property of the material, wherein the tensile strength is above 42.5MPa and can reach 56.9MPa at most; meanwhile, the flame retardant property of the material can reach V-0 level, and the flame retardant containing phosphorus and nitrogen provided by the invention has good flame retardant stability, and the flame retardant property can not be reduced because the flame retardant is dissolved in water in operations such as washing and the like.
The phosphorus-nitrogen-containing flame retardant with hydroxyl prepared by the invention is applied to the preparation of silicon rubber:
examples 7 to 12
A silicone rubber composition is prepared by the following steps:
60 parts by weight of phenyltrimethoxysilane, 60 parts by weight of vinyltrimethoxysilane, 60 parts by weight of phosphorus-nitrogen-containing flame retardant, 20 parts by weight of hydroxyl-terminated PDMS and 10 parts by weight of benzenesulfonic acid are mixed at 60 ℃ for 8 hours, and then 10 parts by weight of catalyst is added to be mixed to obtain the silicone rubber.
The flame retardant is the phosphorus-nitrogen-containing flame retardant with hydroxyl groups provided in preparation examples 1-6 respectively.
Comparative example 4
The only difference from example 7 was that the reactive flame retardant having hydroxyl groups was replaced with 100 parts by weight of polyphosphate.
And (3) performance testing:
the samples provided in examples 7-12 and comparative example 4 were tested for performance by the following method:
(1) combustibility: testing according to UL-94 vertical burning test standard;
(2) tensile strength and elongation: according to the regulation of GB/T528-2009;
(3) flame retardant stability: after soaking the silicone rubber composition in water for 1h, it was dried and its flammability was measured again.
Test results for examples and comparative examples table 2:
TABLE 2
| Sample (I) | Combustibility | Tensile strength/MPa | Elongation at break/% | Combustibility after immersion in water |
| Example 7 | V-0 | 1.5 | 188 | V-0 |
| Example 8 | V-0 | 2.1 | 152 | V-0 |
| Example 9 | V-0 | 1.9 | 158 | V-0 |
| Example 10 | V-0 | 1.8 | 162 | V-0 |
| Example 11 | V-0 | 1.6 | 168 | V-0 |
| Example 12 | V-0 | 1.5 | 171 | V-0 |
| Comparative example 4 | V-0 | 0.9 | 48 | V-1 |
The embodiment and the performance test show that the phosphorus-nitrogen-containing flame retardant with hydroxyl can participate in the preparation of the silicon rubber, and simultaneously, the phosphorus-nitrogen-containing flame retardant with hydroxyl exists as a molecular chain segment, so that the mechanical property of the silicon rubber can be enhanced, wherein the tensile strength is more than 1.5MPa and can reach 2.1MPa at most; the flame retardant property of the material can reach V-0 level; the phosphorus-nitrogen-containing flame retardant provided by the invention has good flame retardant stability, and the flame retardant performance can not be reduced because the flame retardant is dissolved in water in operations such as water washing and the like.
The invention discloses an application of a phosphorus-nitrogen-containing flame retardant with hydroxyl in the preparation of polyester resin, which comprises the following steps:
examples 13 to 18
A polyester composition is prepared by the following steps:
a polyester composition was prepared by mixing 50 parts by weight of maleic anhydride, 10 parts by weight of ethylene glycol, 40 parts by weight of a flame retardant, 50 parts by weight of poly (1, 4-cyclohexylenedimethylene) terephthalate, and 10 parts by weight of polyethylene terephthalate.
The flame retardant is the phosphorus-nitrogen-containing flame retardant with hydroxyl groups provided in preparation examples 1-6 respectively.
Comparative example 5
The only difference from example 13 is that the phosphorus-nitrogen-containing flame retardant having hydroxyl groups was replaced with 40 parts by weight of ethylene glycol.
Comparative example 6
The difference from comparative example 5 is that 30 parts by weight of aluminum tris (diethylphosphinate) were added on the basis of comparative example 5.
And (3) performance testing:
the samples provided in examples 13-18 and comparative examples 5-6 were tested for performance by the following method:
(1) combustibility: testing according to UL-94 vertical burning test standard;
(2) tensile strength and elongation: according to the GB/T1040-2006;
(3) flame retardant stability: after soaking the polyester composition in water for 1h, it was dried and its flammability was measured again.
Test results for examples and comparative examples table 3:
TABLE 3
| Sample (I) | Combustibility | Tensile strength/MPa | Elongation at break/% | Combustibility after immersion in water |
| Example 13 | V-0 | 35.9 | 39 | V-0 |
| Example 14 | V-0 | 45.7 | 24 | V-0 |
| Example 15 | V-0 | 42.2 | 31 | V-0 |
| Example 16 | V-0 | 41.5 | 33 | V-0 |
| Example 17 | V-0 | 40.7 | 36 | V-0 |
| Example 18 | V-0 | 37.2 | 37 | V-0 |
| Comparative example 5 | V-2 | 21.0 | 35 | V-2 |
| Comparative example 6 | V-0 | 32.3 | 29 | V-2 |
As can be seen from the examples and performance tests, the phosphorus-nitrogen-containing flame retardant with hydroxyl can participate in the preparation of polyester, and simultaneously, the phosphorus-nitrogen-containing flame retardant with hydroxyl exists as a molecular chain segment, so that the mechanical property of the polyester composition can be enhanced, wherein the tensile strength is more than 35.9MPa and can reach up to 45.7 MPa; the flame retardant property of the material can reach V-0 level; the phosphorus-nitrogen-containing flame retardant provided by the invention has good flame retardant stability, and the flame retardant performance can not be reduced because the flame retardant is dissolved in water in operations such as water washing and the like.
The applicant states that the present invention is illustrated by the above examples to the phosphorus-nitrogen-containing flame retardant with hydroxyl groups of the present invention, and the preparation method and application thereof, but the present invention is not limited to the above detailed methods, i.e., it does not mean that the present invention must be implemented by relying on the above detailed methods. 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 (9)
1. A phosphorus-nitrogen-containing flame retardant with hydroxyl is characterized by having a structure shown as a formula I:
wherein L is1、L2Each independently selected from a group containing a terminal hydroxyl group;
a is a reactive cyclic group;
Z1、Z2each independently selected from phosphorus-containing groups;
M1selected from linear alkylene, branched alkylene or arylene;
M2selected from any organic group that satisfies a chemical environment;
Y1、Y2each independently selected from an inert group, a sulfur atom, an oxygen atom, or-H;
X1selected from any organylene group that satisfies a chemical environment;
a. b, c, d, f, g and h are respectively and independently selected from integers of 0-5, a and b are not 0 at the same time, f and g are not 0 at the same time, g and h are not 0 at the same time, and meanwhile, b + c + h is less than or equal to 5 and a + d + g is less than or equal to 5;
e is an integer of 0 to 100.
2. The phosphorus-nitrogen flame retardant having hydroxyl group according to claim 1, wherein Z is1、Z2Each independently preferably
X2None or selected from any organylene group, R, satisfying the chemical environment1Is any one of saturated or unsaturated alkyl, aryl or heteroaryl, further preferably methyl, ethyl or phenyl;
preferably, X2Linear or branched alkylene which is free or selected from-NH-or C1-C30;
preferably, X2No or selected from-NH-or C1-C5 linear or branched alkylene.
3. The phosphorus-nitrogen-containing flame retardant having hydroxyl group according to claim 1 or 2, wherein M is1Selected from the group consisting of C1-C30 linear or branched alkylene, C6-C30 arylene, and C5-C7 heteroarylene, more preferably C1-C5 linear alkylene, C3-C5 branched alkylene, or phenyl, still more preferably C1-C3 linear alkylene, C3 branched alkylene, or phenyl.
4. The phosphorus-nitrogen flame retardant having hydroxyl groups according to any one of claims 1 to 3, wherein M is the same as or different from M2Selected from N, S, C1-C30 straight chain or branched chain alkyl, C6-C30 aryl, C5-C7 heteroaryl,
Wherein R is2、R3、R4、R5、R6、R7、R8、R9Each independently of the others is preferably a linear or branched alkylene group having from C1 to C10, L2、Y2、Z2Is connected to R2、R3、R4、R5、R6、R7、R8、R9N, m, i, k are each independently an integer preferably from 0 to 100;
preferably, Y1、Y2Each independently is preferably-H or ═ O.
5. The phosphorus-nitrogen flame retardant having hydroxyl groups according to any one of claims 1 to 4, wherein X is1Selected from N, S, substituted or unsubstituted C1-C30 linear or branched alkylene, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C5-C7 heteroarylene, substituted or unsubstituted C1-C30 alkyleneamine, substituted or unsubstituted C1-C30 alkyleneacyl, substituted or unsubstituted C1-C30 alkyleneester, substituted or unsubstituted C6-C30 alkyleneamine, substituted or unsubstituted C6-C30 aryleneacyl or C6-C30 aryleneester, further preferably substituted or unsubstituted C1-C5 linear or branched alkylene, substituted or unsubstituted C1-C5 alkyleneamine, substituted or unsubstituted C1-C5 alkyleneacyl or substituted or unsubstituted C1-C5 alkyleneester, further preferably-NH-R-, -R '-NH-, -R' -O-, -RV-C (O) -, substituted or unsubstituted C1-C5 linear or branched alkylene, wherein, R, R', R ", RVEach independently is preferably a substituted or unsubstituted C1-C10 straight or branched chain alkylene group.
6. The phosphorus-nitrogen-containing flame retardant having a hydroxyl group according to any one of claims 1 to 5, wherein R is2、R3、R4、R5、R6、R7、R8、R9Each independently is a linear or branched alkylene group preferably having C1-C6;
preferably, n, m, i, k are each independently an integer preferably from 0 to 30.
7. The hydroxyl group-containing phosphorus-nitrogen flame retardant according to any one of claims 1 to 6, wherein the hydroxyl group-containing phosphorus-nitrogen flame retardant is preferably a hydroxyl group-containing phosphorus-nitrogen flame retardant
8. Use of the phosphorus-nitrogen-containing flame retardant having hydroxyl groups according to any of claims 1 to 7 for the preparation of polyurethane resins, phenolic resins, polyester resins, polyamide resins, alkyd resins or silicone rubber resins.
9. A chain extender comprising the phosphorus-nitrogen-containing flame retardant having a hydroxyl group according to any one of claims 1 to 7.
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