CN112898348A - Phosphorus-nitrogen-containing polyether polyol compound, and preparation method and application thereof - Google Patents

Phosphorus-nitrogen-containing polyether polyol compound, and preparation method and application thereof Download PDF

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CN112898348A
CN112898348A CN202110085709.6A CN202110085709A CN112898348A CN 112898348 A CN112898348 A CN 112898348A CN 202110085709 A CN202110085709 A CN 202110085709A CN 112898348 A CN112898348 A CN 112898348A
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phosphorus
nitrogen
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李文木
丁宇林
苏玉苗
杨特平
许明洪
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FUJIAN YUETE NEW MATERIAL TECHNOLOGY CO LTD
Fujian Institute of Research on the Structure of Matter of CAS
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FUJIAN YUETE NEW MATERIAL TECHNOLOGY CO LTD
Fujian Institute of Research on the Structure of Matter of CAS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/6574—Esters of oxyacids of phosphorus
    • C07F9/65742—Esters of oxyacids of phosphorus non-condensed with carbocyclic rings or heterocyclic rings or ring systems
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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

Abstract

The application discloses a phosphorus-nitrogen-containing polyether polyol compound, and a preparation method and application thereof. The phosphorus-nitrogen-containing polyether polyol compound is selected from any one of substances with structural formulas shown in formula I. The compound is used as a phosphorus-nitrogen-containing polyether polyol synergistic flame retardant, can be used as a reactive phosphorus-nitrogen-containing polyether polyol, can be subjected to chemical reaction with isocyanate to generate a carbamate group, and introduces phosphorus and nitrogen as flame retardant elements into a polyurethane network in a covalent bond mode to prepare the phosphorus-nitrogen-containing polyether polyol with excellent flame retardant property. The problems of easy precipitation and migration of the additive flame retardant in the prior art are solved, and the flame retardant has excellent flame retardant performance.

Description

Phosphorus-nitrogen-containing polyether polyol compound, and preparation method and application thereof
Technical Field
The application relates to a phosphorus-nitrogen-containing polyether polyol compound, a preparation method and application thereof, and belongs to the technical field of organic chemical products.
Background
Polyurethane is a high polymer polymerized by polyisocyanate and polyol, and is an important high polymer material; the polyurethane has strong polar carbamate groups and hydrogen bonds in molecules and between molecules, and has excellent properties of high strength, wear resistance, good flexibility, strong adhesive force, low film forming temperature, solvent resistance and the like; meanwhile, the performance of polyurethane materials can be conveniently adjusted in a larger range by changing the types, structures, molecular weights and the like of polyhydroxy compounds, the polyurethane material can be widely applied to industry and daily life and almost permeate into each department of national economy, and the polyurethane material can be prepared into various products such as polyurethane foam, rubber, coating, adhesives, synthetic fibers, synthetic leather, waterproof grouting materials, paving materials and the like, and can be widely applied to various fields such as transportation, buildings, machinery, electronic equipment, furniture, food processing, clothes, textiles, synthetic leather, printing, mining and metallurgy, petrochemical industry, water conservancy, national defense, sports, medical treatment and the like.
Because the polyurethane material structurally has easily combustible hydrocarbon chain segments, the polyurethane material is easy to combust and difficult to self-extinguish when meeting fire, and generates a large amount of smoke dust and toxic gas during combustion, thereby bringing difficulty to extinguishment and simultaneously harming human health and environmental safety. Therefore, to make the polyurethane material more widely used, the flame retardant additive must be added in proper composition and dosage according to the requirement of the material. However, the additive flame retardant has a remarkable influence on mechanical properties, is not good in mixing performance with polyurethane, and is easy to precipitate.
The traditional additive flame retardant in a physical blending mode has the defects of easy occurrence of flame retardant precipitation, migration and the like in the use process of a polyurethane product. The prior art discloses a method for preparing a phosphorus-nitrogen synergistic flame-retardant flexible polyurethane foam plastic by using dihydric alcohol containing phosphorus-nitrogen flame-retardant elements. The prior art also discloses a method for preparing a phosphorus-nitrogen synergistic flame-retardant rigid polyurethane foam plastic by using dihydric alcohol containing phosphorus-nitrogen flame-retardant elements. The defects of using the traditional additive flame retardant in a physical blending mode are avoided, and the compulsory compatible and synergistic flame-retardant polyurethane material is formed. However, structurally, the aromatic ring structure contained in the polyurethane material can seriously affect the mechanical properties of the polyurethane material; the phosphorus content of the structure is low, a large amount of flame retardant is required to be added to achieve a certain flame retardant effect, and the addition of the structure has great influence on the regulation of the proportion of the soft segment and the hard segment of the polyurethane, so that the regulation of the molecular structure is not facilitated; moreover, the synthesis of the flame retardant is complex and is not beneficial to large-scale synthesis; the flame retardant is a simple condensed phase flame retardant mechanism on the flame retardant mechanism, and the flame retardant effect is good without the flame retardant effect of an intumescent flame retardant.
Disclosure of Invention
According to one aspect of the application, the phosphorus-nitrogen-containing polyether polyol compound is used as a phosphorus-nitrogen-containing polyether polyol synergistic flame retardant, and can be used as a reactive phosphorus-nitrogen-containing polyether polyol to perform a chemical reaction with isocyanate to generate a urethane group, and phosphorus and nitrogen serving as flame retardant elements are introduced into a polyurethane network in a covalent bond mode to prepare the phosphorus-nitrogen-containing polyether polyol with excellent flame retardant property. The problems of easy precipitation and migration of the additive flame retardant in the prior art are solved, and the flame retardant has excellent flame retardant performance.
A phosphorus-nitrogen-containing polyether polyol compound is selected from any one of substances with a structural formula shown in a formula I;
Figure BDA0002910677840000021
in formula I, R1、R2、R3、R4Independently selected from hydrogen, C1～C4Any of alkyl groups;
the R is5Any one selected from the group having the structural formula shown in formula II;
Figure BDA0002910677840000031
in formula II, R51Is selected from C1～C9Alkylene radical, C1～C9Any of substituted alkylene groups;
R52、R53independently selected from C1～C10Alkylene radical, C1～C10Any of substituted alkylene groups.
Alternatively, in formula II, R52Is selected from C1～C6Alkylene radical, C1～C6Any of substituted alkylene groups;
R53is selected from C1～C10Alkylene radical, C1～C10Any of substituted alkylene groups.
In the application, the phosphorus-nitrogen-containing polyether polyol compound refers to a compound which contains phosphorus and nitrogen elements at the same time, and the end group of the compound contains 2 hydroxyl groups (-OH).
Preferably, in formula I, R3And R4Selected from hydrogen.
Alternatively, in formula II, R51Is selected from C1～C9Straight chain alkylene group, C2～C9Branched alkylene group, C1～C9Any of substituted alkylene groups;
R52、R53independently selected from C1～C10Straight chain alkylene group, C2～C10Branched alkylene group, C1～C10Any of substituted alkylene groups.
Specifically, in formula II, R51Is selected from C1～C9Straight chain alkylene group, C2～C9Branched alkylene group, C1～C5Any of substituted alkylene groups;
R52is selected from C1～C6Straight chain alkylene group, C2～C6Branched alkylene group, C1～C6Any of substituted alkylene groups;
R53is selected from C1～C10Straight chain alkylene group, C2～C10Branched alkylene group, C1～C10Any of substituted alkylene groups.
Alternatively, the R is51Any one of the groups with structural formulas shown as formulas II-11, II-12 and II-13 is selected;
Figure BDA0002910677840000032
in the formula II-11, R511Is selected from C1～C4Any of linear alkylene groups;
Figure BDA0002910677840000041
in the formula II-12, R512、R513Independently selected from C1～C4Any of alkyl groups;
Figure BDA0002910677840000042
in the formula II-13, R514Is selected from C1～C4Any of alkyl groups.
Preferably, in the formula II-11, R511Selected from methylene.
Preferably, in formula II-12, R512、R513Any one selected from methyl.
Preferably, in formula II-13, R514Selected from methyl.
Alternatively, the R is52Any one of groups with structural formulas shown as formulas II-21 and II-22;
*-R521- (O-X-O) -formula II-21
In the formula II-21, R521Is selected from C1～C4Any of linear alkylene groups;
Figure BDA0002910677840000044
in the formula II-22, R522Is selected from C1～C4Any of alkyl groups.
Preferably, in the formula II-21, R521Selected from methylene and ethylene.
Preferably, in formula II-22, R522Selected from methyl.
Alternatively, the R is53Any one of the groups with structural formulas shown as formulas II-31, II-32 and II-33;
*-R531- (O) formula II-31
In the formula II-31, R531Is selected from C1～C4Any of linear alkylene groups;
Figure BDA0002910677840000052
in the formula II-32, R532、R533Independently selected from C1～C4Any of alkyl groups;
Figure BDA0002910677840000053
in the formula II-33, R534Is selected from C1～C4Any of linear alkylene groups;
R535is selected from C1～C4Any of alkyl groups.
Preferably, in formula II-31, R531Selected from any one of methylene and ethylene.
Preferably, in the formulae II-32, R532、R533Independently selected from methyl.
Preferably, in the formula II-33, R534Selected from methylene, R535Selected from methyl.
Optionally, the phosphorus-nitrogen-containing polyether polyol compound is selected from any one of substances with structural formulas shown in formulas I-1, I-2, I-3 and I-4;
Figure BDA0002910677840000054
Figure BDA0002910677840000061
Figure BDA0002910677840000062
Figure BDA0002910677840000063
preferably, the phosphorus and nitrogen containing polyether polyol compound has a structural formula shown in formula a:
Figure BDA0002910677840000071
in formula a, A1、A2Independently selected from any one of H and methyl;
A3any one selected from H and methyl;
A4is selected from methylene;
A5selected from any one of H and methyl.
According to the second aspect of the application, the preparation method of the phosphorus-nitrogen-containing polyether polyol compound is further provided, materials containing a cyclic phosphorus compound and a cyclic nitrogen oxide compound are reacted in the presence of a catalyst, and the phosphorus-nitrogen-containing polyether polyol compound can be obtained;
wherein the cyclic phosphorus compound contains a P-H bond;
the ring of the cyclic nitrogen-oxygen compound contains N atoms and O atoms;
the catalyst is selected from any one of strong acid cation resins.
Specifically, the strong acid cation resin is D001.
Optionally, the cyclic phosphorus compound is selected from any one of substances having a structural formula shown in formula III;
Figure BDA0002910677840000072
in formula III, R1、R2、R3、R4Independently selected from hydrogen, C1～C4Any of alkyl groups.
Preferably, R3And R4Selected from hydrogen.
Specifically, the cyclic phosphorus compound is selected from any one of substances having a structural formula shown in formula III-1;
Figure BDA0002910677840000081
a method for preparing a cyclic phosphorus compound represented by formula III;
1) reacting raw materials of a polyalcohol compound, a monohydric alcohol compound and a phosphorus-containing compound for 12-48 hours at low temperature to obtain a mixture containing the cyclic phosphorus compound;
2) reacting the mixture containing the cyclic phosphorus compound obtained in the step 1) under the inert gas atmosphere and heating for 12-48 hours to obtain a further purified mixture containing the cyclic phosphorus compound;
3) distilling at 120-160 ℃ under reduced pressure to obtain the cyclic phosphorus compound.
Preferably, the specific reaction conditions in step 1) are: and uniformly mixing the polyalcohol compound, the monohydric alcohol compound and the phosphorus-containing compound at a low temperature for reaction, heating the mixture for reaction in an atmosphere containing inactive gas, and distilling the mixture under reduced pressure to obtain a substance with a structural formula III.
The polyalcohol compound has a structural formula shown in a formula c:
Figure BDA0002910677840000082
in formula c, R'71，R'72Independently selected from one of hydrogen and alkyl; r'73，R'74Independently selected from one of alkylene.
In the formula c, R'71，R'72Independently selected from hydrogen, C1～C4One of alkyl groups; further preferably, R'71，R'72Independently selected from hydrogen, C1～C4One of alkyl groups;
R'73，R'74is independently selected from C1～C4One of alkylene and hydrogen; further preferably, R'73，R'74Is independently selected from one of methylene and hydrogen.
The monohydric alcohol compound has a structural formula shown in formula b:
Figure BDA0002910677840000091
in formula b, R'81，R'82Independently selected from one of hydrogen and alkyl.
Preferably, R 'in the formula b'81，R'82Independently selected from hydrogen, C1～C4One of alkyl groups; more preferably, R 'in the formula b'81，R'82Independently selected from one of hydrogen and methyl.
The phosphorus-containing compound comprises phosphorus trichloride and phosphorus oxychloride.
Preferably, the mass ratio of the polyalcohol compounds, the monohydric alcohol compounds and the phosphorus-containing compounds in the step 1) is 1: 1-5: 1-8;
preferably, the mass ratio of the polyol compound, the alcohol compound and the phosphorus-containing compound in the step 1) is 1: 1-3: 1 to 5.
Preferably, the low-temperature condition in the step 1) is 0-30 ℃ for 12-40 hours;
preferably, the low-temperature condition in the step 1) is 10-30 ℃ for 15 hours;
preferably, the heating condition in the step 2) is 80-130 ℃ for 12-40 hours;
preferably, the heating condition in step 2) is 80-130 ℃ for 15 hours.
Optionally, the cyclic nitrogen oxide compound is selected from any one of substances with a structural formula shown in a formula IV;
Figure BDA0002910677840000092
in the formula IV, R in the formula IV51、R52、R53Is selected as in formula II.
Specifically, in formula IV, R51Is selected from C1～C9Alkylene radical, C1～C9Any of substituted alkylene groups;
in the formula IV, R52Is selected from C1～C6Alkylene radical, C1～C6Any of substituted alkylene groups;
in the formula IV, R53Is selected from C1～C10Alkylene radical, C1～C10Any of substituted alkylene groups.
Alternatively, in formula IV, the R51Is selected from any one of groups with structural formulas shown as formulas II-11, II-12 and II-13.
Specifically, in formula IV, R51Any one selected from the group of the following structural formulae;
*-R511- (O-X-O) -formula II-11
In the formula II-11, R511Is selected from C1～C4Any of linear alkylene groups;
Figure BDA0002910677840000102
in the formula II-12, R512、R513Independently selected from C1～C4Any of alkyl groups;
Figure BDA0002910677840000103
in the formula II-13, R514Is selected from C1～C4Any of alkyl groups.
Preferably, in the formula II-11, R511Selected from methylene.
Preferably, in formula II-12, R512、R513Selected from methyl.
Preferably, in formula II-13, R514Selected from methyl.
Alternatively, in formula IV, R52Is selected from any one of groups with structural formulas shown in formulas II-21 and II-22.
Specifically, in formula IV, R is52Any one of groups with structural formulas shown as formulas II-21 and II-22;
*-R521- (O-X-O) -formula II-21
In the formula II-21, R521Is selected from C1～C4Any of linear alkylene groups;
Figure BDA0002910677840000112
in the formula II-22, R522Is selected from C1～C4Any of alkyl groups.
Preferably, in the formula II-21, R521Selected from methylene and ethylene.
Preferably, in formula II-22, R522Selected from methyl.
Alternatively, in formula IV, the R53Is selected from any one of groups with structural formulas shown as formulas II-31, II-32 and II-33.
Specifically, in formula IV, R is53Any one selected from the group having a structural formula shown by the following formula;
*-R531- (O) formula II-31
In the formula II-31, R531Is selected from C1～C4Any of linear alkylene groups;
Figure BDA0002910677840000114
in the formula II-32, R532、R533Independently selected from C1～C4Any of alkyl groups;
Figure BDA0002910677840000115
in the formula II-33, R534Is selected from C1～C4Any of linear alkylene groups;
R535is selected from C1～C4Any of alkyl groups.
Preferably, in formula II-31, R531Selected from any one of methylene and ethylene.
Preferably, in the formulae II-32, R532、R533Independently selected from methyl.
Preferably, in the formula II-33, R534Selected from methylene, R535Selected from methyl.
Optionally, the cyclic nitrogen oxide compound is selected from any one of substances with structural formulas shown as a formula IV-1, a formula IV-2, a formula IV-3 and a formula IV-4;
Figure BDA0002910677840000121
Figure BDA0002910677840000122
Figure BDA0002910677840000123
Figure BDA0002910677840000131
preferably, the cyclic nitroxide compound is at least one selected from the group consisting of compounds having the structure represented by formula b:
Figure BDA0002910677840000132
in formula b, A7 and A8 are independently selected from C1～C4One of alkyl and hydrogen;
a6 is selected from C1～C4One of alkylene groups.
The method for preparing the ring nitrogen compound at least comprises the following steps: :
a. sequentially adding 1 part of alcohol amine compound and 1-8 parts of aldehyde group compound into a 500mL three-neck flask according to mass fraction, stirring and reacting for 1-8 hours at 20-60 ℃ in an inert gas atmosphere, and then heating to 70-100 ℃ and distilling under reduced pressure for 1-8 hours to obtain the cyclic nitrogen compound.
b. According to the mass fraction agent, 1 part of alcohol amine compound is dissolved in a proper amount of isopropanol solvent, 1-8 parts of aldehyde compound is dissolved in a proper amount of toluene, the mixture is heated and refluxed for 15-20 hours under the atmosphere of inactive gas, and then the reaction solvent is evaporated. The cyclic nitrogen compound is obtained by reduced pressure distillation for 2-6 hours.
Optionally, the mass parts of the materials are as follows:
100-200 parts of a cyclic phosphorus compound;
100 portions and 150 portions of cyclic nitrogen oxide.
Preferably, the mass parts of the materials are as follows:
170 parts of cyclic phosphorus compound 140;
100 portions and 150 portions of cyclic nitrogen oxide.
Optionally, the reaction conditions are: the reaction temperature is 30-70 ℃; the reaction time is 2-20 h.
Preferably, the reaction conditions are: the reaction temperature is 40-65 ℃; the reaction time is 2-15 h.
According to a third aspect of the present application, there is also provided a flame retardant, wherein the flame retardant comprises at least one of the phosphorus-nitrogen-containing polyether polyol compound described in any one of the above and the phosphorus-nitrogen-containing polyether polyol compound obtained by the preparation method described in any one of the above.
According to a fourth aspect of the application, a flame retardant polyurethane is also provided, and the flame retardant polyurethane is prepared from the flame retardant.
Specifically, the flame-retardant polyurethane is prepared from a raw material containing a phosphorus-nitrogen-containing polyether polyol compound.
According to a fifth aspect of the present application, there is also provided a method of preparing a flame retardant polyurethane, comprising:
reacting materials containing polyether polyol, polyisocyanate and a flame retardant in the presence of a catalyst to obtain the flame-retardant polyurethane;
the catalyst comprises catalyst a and/or catalyst b;
the catalyst a is selected from any one of organic tin salts;
the catalyst b is selected from any one of silicone oil.
Preferably, the flame-retardant polyurethane is obtained by reacting a raw material containing a phosphorus-nitrogen-containing polyether polyol compound under the condition of a catalyst at 50-180 ℃ for 1-60min for polymerization.
Preferably, the reaction condition is 70-130 ℃ for 1-50 min.
Preferably, the catalyst a is selected from at least one of organotin salts.
Preferably, the catalyst a is tin isooctanoate.
Preferably, the polyether polyol is at least one selected from polyethylene glycol diol, polypropylene glycol diol and polytetrahydrofuran diol.
Preferably, the molecular weight of the polyether polyol is 600-5000 Da. Further preferably, the molecular weight of the polyether polyol is 1000-3000 Da.
The polyisocyanate is selected from Toluene Diisocyanate (TDI), 1, 4-tetramethyleneMethyl diisocyanate, 1, 6-Hexamethylene Diisocyanate (HDI), 1, 12-dodecamethylene diisocyanate, cyclohexane-1, 3-or 1, 4-diisocyanate, isophorone diisocyanate (IPDI), diphenylmethane 4, 4-diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), 1, 6-Hexamethylene Diisocyanate (HDI), polymethylene polyphenyl isocyanates (PAPI), Xylylene Diisocyanate (XDI), naphthalene-1, 5-diisocyanate (NDI), methylcyclohexyl diisocyanate (HTDI), tetramethylxylylene diisocyanate (TMXDI), hydrogenated phenylmethane diisocyanate (H12MDI).
Preferably, the polyisocyanate is selected from isophorone diisocyanate (IPDI), Toluene Diisocyanate (TDI), 1, 6-Hexamethylene Diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), diphenylmethane 4, 4-diisocyanate (MDI), Toluene Diisocyanate (TDI), hydrogenated phenylmethane diisocyanate (H)12MDI).
Preferably, the catalyst is selected from at least one of organotin salts.
Preferably, the catalyst is tin isooctanoate.
Preferably, the reaction condition is that the reaction is carried out for 1-40 minutes at 80-120 ℃.
Preferably, the mass part ratio of the polyether polyol, the phosphorus-nitrogen-containing polyether polyol compound, the isocyanate and the catalyst is 10-50: 5-50: 2-100: 0.1 to 0.3.
Preferably, the mass part ratio of the polyether polyol, the phosphorus-nitrogen-containing polyether polyol compound, the isocyanate and the catalyst is 15-30: 10-35: 20-60: 0.1 to 0.3.
Optionally, the material further comprises at least one of polyester polyol, small molecule polyol and small molecule polyamine;
wherein the small molecule polyol is selected from C1～C6At least one of a polyol;
the small molecule polyamine is selected from C1～C6At least one of polyamines.
As a preferred embodiment, the process for the preparation of flame retardant polyurethanes comprises at least the following steps:
polyether polyol, polyether polyol compound containing phosphorus and nitrogen, isocyanate and a catalyst are mixed and react for 1-50min at 70-130 ℃ to obtain polyurethane.
According to the sixth aspect of the application, a polyurethane product is also provided, wherein the polyurethane product contains the flame-retardant polyurethane and the flame-retardant polyurethane prepared by the method.
Optionally, the polyurethane product comprises at least one of a polyurethane elastomer, a polyurethane foam, an aqueous polyurethane body.
According to the seventh aspect of the application, the application of the polyurethane product in the fields of heat insulation materials, packaging materials, coatings, adhesives and leather is also provided.
In the present application, the inert gas atmosphere is selected from at least one of nitrogen, helium, neon and argon.
In this application, C1～C2、C1～C4And the like refer to the number of carbon atoms that the group contains.
"alkyl" is a group formed by the loss of any one hydrogen atom from the molecule of an alkane compound including straight-chain alkanes, branched-chain alkanes, cyclic alkanes, branched-chain cyclic alkanes;
"alkylene" is a group formed by the loss of any two hydrogen atoms from an alkane compound molecule;
"substituted alkylene" refers to a group in which any hydrogen atom on the alkylene is replaced with a substituent.
The beneficial effects that this application can produce include:
the phosphorus-nitrogen-containing polyether polyol compound and the preparation method thereof have the advantages that the method is simple to operate, and the raw material source is wide; by introducing the phosphorus-containing unit and the nitrogen-containing unit into the polyol by the method, the polyurethane prepared by the method has excellent flame retardant property and mechanical property.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum hydrogen spectrum of a phosphorus-epoxy polyol compound D1 in example 2 herein;
FIG. 2 is a schematic illustration of the synthesis of a phosphorus and nitrogen containing polyether polyol according to the present application;
FIG. 3 is a stress-strain curve of the tensile test of example 3 of the present application;
FIG. 4 shows the burned morphology of example 4 of the present application.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials and catalysts in the examples of the present application were all purchased commercially.
The analysis method in the examples of the present application is as follows:
and (4) carrying out oxygen index test by using a JF-3 oxygen index combustor.
NMR spectroscopy was performed using AVANCE III HD (Bruker-BioSpin).
Tensile compression tests were performed using a S2015HX0239 universal materials tester.
EXAMPLE 1 preparation of the Cyclophosph Compound C1
A500 mL three-necked flask equipped with a stirrer, a reflux condenser and a nitrogen gas injection tube was charged with 34.8g of 2-ethylhexanol and 31.4g of a polyol compound (2, 2-dimethyl-1, 3-propanediol), and 41.3g of a phosphorus-containing compound (phosphorus trichloride) was slowly added dropwise at a low temperature (15 ℃ C.), followed by a reaction at a normal temperature (25 ℃ C.) for 15 hours and then a vapor bath reaction for 15 hours. The mixture obtained in the above reaction was placed in
Figure BDA0002910677840000171
In a vacuum distillation device, the product of the cyclic phosphorus compound 2, 2-dimethyl-1, 3-propanediol cyclic hydrogen phosphate is marked as C1 at 120 ℃. The structural formula is shown as the following formula.
Example 2 Synthesis of phosphorus and nitrogen-containing polyether polyol D1
150g of the cyclic phosphorus compound of example 1, 117g of 2- (oxazolidin-3-yl) ethanol (i.e., cyclic nitrogen oxide) and 2.2g of a macroporous, strongly acidic cationic resin as a catalyst were charged in a 500mL four-necked flask equipped with a stirrer and a nitrogen-injecting tube, and the mixture was heated to 42 ℃ and then incubated at 42 ℃ for 4 hours. Wherein the epoxy polyol compound is D1.
The nuclear magnetic test was performed on the epoxy polyol compound D1, and the test results are shown in fig. 1.
It can be seen that the structural formula of the epoxy resin compound D1 is:
Figure BDA0002910677840000172
example 3 Synthesis of phosphorus and nitrogen-containing polyether polyol D2
150g of the cyclic phosphorus compound of example 1, 145.2g of 2- (2, 5-dimethyl-1, 3-oxazolidin-3-yl) ethanol (i.e., cyclic nitrogen oxide compound) and 2.2g of a macroporous strongly acidic cation resin as a catalyst were charged in a 500mL four-necked flask equipped with a stirrer and a nitrogen gas injection tube, and the mixture was heated to 50 ℃ and allowed to react at 50 ℃ for 4 hours. Wherein the epoxy polyol compound is D2, and the structural formula is as follows:
Figure BDA0002910677840000181
example 4 preparation of polyurethane J1
10g of polyol prepolymer (self-made, please refer to CN 105713168B), 2g of phosphorus-nitrogen-containing polyether polyol D1, 3 drops of silicone oil (specifically, surfactant with molecular mass of 1000) and 3 drops of catalyst (specifically, tin isooctanoate) are mixed, then 10g of isocyanate (self-made, please refer to CN 105924611B) is added for mixing, and the mixture is heated at 110 ℃ for 50min to obtain polyurethane flexible foam J1.
Example 5 preparation of polyurethane K1
10g of polyol prepolymer (self-made, please refer to CN 105713168B), 2g of phosphorus-nitrogen-containing polyether polyol D2, 3 drops of silicone oil (specifically, surfactant with molecular mass of 1000) and 3 drops of catalyst (specifically, tin isooctanoate) are mixed, then 10g of isocyanate (self-made, please refer to CN 105924611B) is added for mixing, and the mixture is heated at 110 ℃ for 20min to obtain the polyurethane flexible foam K1.
Example 6 flame retardancy test
The flame retardancy of samples J1 and K1 was measured according to the method in GB/T2408-2008 standard (burning test standard), and the results are shown in Table 1.
TABLE 1 flame retardancy oxygen index number oxygen index test of samples J1, K1
Sample numbering LOI value
J1 23.7
K1 25.8
As can be seen from Table 1, the flame retardant polyurethanes J1 and K1 prepared have excellent flame retardant effect.
FIG. 4 shows the appearance of the polyurethane K1 after burning, and it can be seen that the flame retardant forms a coke layer after burning, thereby protecting the polyurethane elastomer material.
Example 7 mechanical Property testing
The sample J1 is subjected to mechanical property test; the tensile properties were determined by the method described in GB/T13022-91. The tensile test stress strain curve is shown in fig. 3. As can be seen from FIG. 3, the prepared flame retardant polyurethane J1 has excellent mechanical properties.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.

Claims (10)

1. The phosphorus-nitrogen-containing polyether polyol compound is characterized in that the phosphorus-nitrogen-containing polyether polyol compound is selected from any one of substances with structural formulas shown in formula I;
Figure FDA0002910677830000011
in formula I, R1、R2、R3、R4Independently selected from hydrogen, C1～C4Any of alkyl groups;
the R is5Any one selected from the group having the structural formula shown in formula II;
Figure FDA0002910677830000012
in formula II, R51Is selected from C1～C9Alkylene radical, C1～C9Any of substituted alkylene groups;
R52、R53independently selected from C1～C10Alkylene radical, C1～C10Any of substituted alkylene groups.
2. The phosphorus-nitrogen-containing polyether polyol compound according to claim 1, wherein in formula II, R is51Is selected from C1～C9Straight chain alkylene group, C2～C9Branched alkylene group, C1～C9Any of substituted alkylene groups;
R52、R53independent of each otherIs selected from C1～C10Straight chain alkylene group, C2～C10Branched alkylene group, C1～C10Any of substituted alkylene groups;
preferably, said R is51Any one of the groups with structural formulas shown as formulas II-11, II-12 and II-13 is selected;
*-R511- (O-X-O) -formula 11-11
In the formula II-11, R511Is selected from C1～C4Any of linear alkylene groups;
Figure FDA0002910677830000021
in the formula II-12, R512、R513Independently selected from C1～C4Any of alkyl groups;
Figure FDA0002910677830000022
in the formula II-13, R514Is selected from C1～C4Any of alkyl groups;
preferably, said R is52Any one of groups with structural formulas shown as formulas II-21 and II-22;
*-R521- (II) -21
In the formula II-21, R521Is selected from C1～C4Any of linear alkylene groups;
Figure FDA0002910677830000023
in the formula II-22, R522Is selected from C1～C4Any of alkyl groups;
preferably, said R is53Any one of the groups with structural formulas shown as formulas II-31, II-32 and II-33;
*-R531- (O-X-O) -formula 11-31
In the formula II-31, R531Is selected from C1～C4Any of linear alkylene groups;
Figure FDA0002910677830000031
in the formula II-32, R532、R533Independently selected from C1～C4Any of alkyl groups;
Figure FDA0002910677830000032
in the formula II-33, R534Is selected from C1～C4Any of linear alkylene groups;
R535is selected from C1～C4Any of alkyl groups.
3. The method for preparing the phosphorus-nitrogen-containing polyether polyol compound according to claim 1 or 2, characterized in that a material containing a cyclic phosphorus compound and a cyclic nitrogen oxide compound is reacted in the presence of a catalyst to obtain the phosphorus-nitrogen-containing polyether polyol compound;
wherein the cyclic phosphorus compound contains a P-H bond;
the ring of the cyclic nitrogen-oxygen compound contains N atoms and O atoms;
the catalyst is selected from any one of strong acid cation resin;
preferably, the cyclic phosphorus compound is selected from any one of substances with a structural formula shown in a formula III;
Figure FDA0002910677830000033
in formula III, R1、R2、R3、R4Independent of each otherIs selected from hydrogen and C1～C4Any of alkyl groups;
preferably, the cyclic nitrogen oxide compound is selected from any one of substances with a structural formula shown in a formula IV;
Figure FDA0002910677830000041
in the formula IV, R51、R52、R53Is selected as in formula II;
preferably, R51Is selected from C1～C9Straight chain alkylene group, C2～C9Branched alkylene group, C1～C5Any of substituted alkylene groups;
R52is selected from C1～C6Straight chain alkylene group, C1～C6Branched alkylene group, C1～C5Any of substituted alkylene groups;
R53is selected from C1～C10Straight chain alkylene group, C2～C10Branched alkylene group, C1～C6Any of substituted alkylene groups;
preferably, in formula IV, R is51Any one of the groups with structural formulas shown as formulas II-11, II-12 and II-13 is selected;
preferably, in formula IV, R is52Any one of groups with structural formulas shown as formulas II-21 and II-22;
preferably, in formula IV, R is53Is selected from any one of groups with structural formulas shown as formulas II-31, II-32 and II-33.
4. The preparation method according to claim 3, characterized in that, in the material, by mass:
100-200 parts of a cyclic phosphorus compound;
100 portions and 150 portions of cyclic nitrogen oxide.
5. The method according to claim 3, wherein the reaction conditions are as follows: the reaction temperature is 30-70 ℃; the reaction time is 2-20 h;
preferably, the reaction conditions are: the reaction temperature is 40-65 ℃; the reaction time is 2-15 h.
6. A flame retardant, characterized in that the flame retardant comprises at least one of the phosphorus-nitrogen-containing polyether polyol compound according to any one of claims 1 or 2 and the phosphorus-nitrogen-containing polyether polyol compound obtained by the production method according to any one of claims 3 to 5.
7. A flame retardant polyurethane prepared from the flame retardant of claim 6.
8. The method of making a flame retardant polyurethane of claim 7, wherein the method comprises:
reacting materials containing polyether polyol, polyisocyanate and a flame retardant in the presence of a catalyst to obtain the flame-retardant polyurethane;
the catalyst comprises catalyst a and/or catalyst b;
the catalyst a is selected from any one of organic tin salts;
the catalyst b is selected from any one of silicone oil;
preferably, the material also comprises at least one of polyester polyol, small molecule polyol and small molecule polyamine;
wherein the small molecule polyol is selected from C1～C6At least one of a polyol;
the small molecule polyamine is selected from C1～C6At least one of polyamines.
9. A polyurethane product comprising at least one of the flame retardant polyurethane of claim 7, the flame retardant polyurethane prepared by the process of claim 8;
preferably, the polyurethane product comprises at least one of a polyurethane elastomer, a polyurethane foam, an aqueous polyurethane body.
10. Use of the polyurethane product as claimed in claim 9 in the field of insulation materials, packaging materials, coatings, adhesives, leather.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3746572A (en) * 1971-02-23 1973-07-17 Stauffer Chemical Co Process for flame retarding fabrics
US3969437A (en) * 1971-02-23 1976-07-13 Stauffer Chemical Company Cyclic phosphorus esters
CN105713168A (en) * 2016-05-04 2016-06-29 中国科学院福建物质结构研究所 Polyurethane prepolymer and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3746572A (en) * 1971-02-23 1973-07-17 Stauffer Chemical Co Process for flame retarding fabrics
US3969437A (en) * 1971-02-23 1976-07-13 Stauffer Chemical Company Cyclic phosphorus esters
CN105713168A (en) * 2016-05-04 2016-06-29 中国科学院福建物质结构研究所 Polyurethane prepolymer and preparation method thereof

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