CN107686547B - Flame retardant polyurethane and preparation method thereof - Google Patents

Flame retardant polyurethane and preparation method thereof Download PDF

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CN107686547B
CN107686547B CN201710917397.4A CN201710917397A CN107686547B CN 107686547 B CN107686547 B CN 107686547B CN 201710917397 A CN201710917397 A CN 201710917397A CN 107686547 B CN107686547 B CN 107686547B
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flame retardant
polyether polyol
phosphorus
formula
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CN107686547A (en
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夏建荣
李文木
苏玉苗
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Fujian Institute of Research on the Structure of Matter of CAS
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    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5075—Polyethers having heteroatoms other than oxygen having phosphorus
    • C08G18/509—Polyethers having heteroatoms other than oxygen having phosphorus having nitrogen in addition to phosphorus
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
    • C08G65/33303—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
    • C08G65/3331—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group cyclic
    • C08G65/33313—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group cyclic aromatic
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
    • C08G65/33303—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
    • C08G65/33317—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group heterocyclic
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/335—Polymers modified by chemical after-treatment with organic compounds containing phosphorus
    • C08G65/3353—Polymers modified by chemical after-treatment with organic compounds containing phosphorus containing oxygen in addition to phosphorus
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/335—Polymers modified by chemical after-treatment with organic compounds containing phosphorus
    • C08G65/3353—Polymers modified by chemical after-treatment with organic compounds containing phosphorus containing oxygen in addition to phosphorus
    • C08G65/3355—Polymers modified by chemical after-treatment with organic compounds containing phosphorus containing oxygen in addition to phosphorus having phosphorus bound to carbon and oxygen
    • 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
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation

Abstract

This application discloses a kind of flame retardant polyurethanes, are prepared by the raw material containing phosphorus-nitrogen containing polyether polyol；Ignition-proof element phosphorus nitrogen introduces polyurethane network in the form of covalent bond in the flame retardant polyurethane, as additive flame retardant for avoiding the deficiencies of physical blending additive flame retardant is easily precipitated, migrates in flame retardant polyurethane.

Description

Flame retardant polyurethane and preparation method thereof
Technical field
This application involves a kind of flame retardant polyurethanes and preparation method thereof, belong to fire proofing field.
Background technique
Polyurethane is the high polymer as made of polyisocyanates and polymerization, is a kind of important high molecular material； Highly polar carbamate groups and hydrogen bond are existed simultaneously with intermolecular in the molecule, there is high-intensitive, wear-resisting, flexibility The excellent properties such as good, adhesive force is strong, film-forming temperature is low, solvent resistant；Simultaneously by change the type of polyol, structure, Molecular weight etc. can also be conveniently adjusted the performance of polyurethane material in a big way, be widely used in industrial and daily In life, and each department of national economy is almost penetrated into, polyurethane foam plastics, rubber, coating, bonding can be made in it The multiple products such as agent, synthetic fibers, synthetic leather, water-proof grouting agent, pavement material, be widely used in communications and transportation, building, Machinery, electronic equipment, furniture, food processing, clothes, weaving, synthetic leather, printing, mining and metallurgy, petrochemical industry, water conservancy, national defence, The numerous areas such as sport, medical treatment.
Since polyurethane material has incendive hydrocarbon segment in structure, burning and difficult self-extinguishment, combustion are easy when meeting fire A large amount of flue dust and toxic gas are generated when burning, human health and environment peace can also be jeopardized by bringing to fire extinguishing while difficulty Entirely.Therefore, to be more widely applied polyurethane material, suitable component and dosage must just be added according to the requirement of material Flame-retardant additive.However, additive flame retardant is more apparent to mechanical property, bad with polyurethane mixed performance, fire retardant is easy It is precipitated.106117600 A of Chinese patent CN discloses a kind of reactive flame retardant THPP, which there is preferable phosphorus to contain Amount and carbon left have the characteristics such as flame retarding efficiency height and Halogen, low cigarette, low toxicity, durability.104448202 A of Chinese patent CN A kind of phosphor-containing flame-proof method for preparing thermoplastic polyurethane elastomer is disclosed, the disclosure technology is with molecular weight for 1500~2500 Phosphorous-containing polyester dihydric alcohol be raw material, in polyurethane elastomer material strand introduce ignition-proof element phosphorus, reduce it is inorganic fire-retarded The addition of agent, so that the fire-retardant oxygen index (OI) of material is increased to 32 by 19, flame retardant property is good.
Since hydrolysis easily occurs for the ester bond in polyester, the polyurethane water resistance as obtained by polyester polyol is caused to owe It is good.In many application fields, for polyurethane, it is often necessary to this class feature.For example, for can be by polyether polyol system Standby polyurethane, it is desirable to its excellent anti-hydrolytic performance is assigned, as 103703052 B of Chinese patent CN discloses a kind of prepare The method of polyether carbonate polyol, the polyether carbonate polyol as made from the technology are applied to polyurethane field with excellent Performance.Wherein in the first step, by one or more H- function starter substances, by one or more alkylene oxides and titanium dioxide Carbon prepares polyether carbonate polyol in the presence of at least one DMC- catalyst, and in second step, at least two differences Alkylene oxide mixture in the presence of at least one DMC- catalyst to polyether carbonate polyol carry out chain.It is for another example Chinese 103314031 B of patent CN discloses a kind of hydrophobic polyether ester polyol, the polyester ether polylol application as made from the technology There is excellent anti-hydrolytic performance in polyurethane field.
Additive flame retardant of the tradition in a manner of physical blending, in polyurethane products use process, Yi Fasheng fire retardant The defects of being precipitated, migrating.The dihydric alcohol preparation that 106496505 A of Chinese patent CN is disclosed with a kind of phosphorus-nitrogen containing ignition-proof element A kind of method of the flexible polyurethane foam of phosphorus nitrogen cooperative flame retardant.106496507 A of Chinese patent CN is disclosed with one kind The method that the dihydric alcohol of phosphorus-nitrogen containing ignition-proof element prepares a kind of rigid polyurethane foam of phosphorus nitrogen cooperative flame retardant.Avoiding makes With the deficiency of additive flame retardant of the tradition in a manner of physical blending, is formed and force compatible, cooperative flame retardant polyurethane foam Plastics.
Summary of the invention
According to the one aspect of the application, a kind of flame retardant polyurethane is provided, which overcome fire retardant in the prior art is easy The problem of being precipitated, migrating, has excellent flame retardant property.
The flame retardant polyurethane is prepared by the raw material containing phosphorus-nitrogen containing polyether polyol；
The phosphorus-nitrogen containing polyether polyol is selected from least one of the compound with the chemical formula as shown in formula (I):
Wherein, A00Selected from C1~C3One of alkylidene；
R01, R02, R03, R04Independently selected from one of hydrogen, alkyl；
R05, R06, R07, R08, R09, R10, R11, R12, R13Independently selected from hydrogen, C1~C4One of alkyl；
R14Selected from one of group shown in formula (II), formula (III), formula (IV):
R in formula (II)21, R22, R23, R24, R25Independently selected from C1~C4One of alkyl, hydrogen, amino；
R in formula (III)31, R32, R33Independently selected from C1~C4One of alkyl, hydrogen, amino；
R in formula (IV)41, R42Independently selected from C1~C4One of alkyl, hydrogen, amino.
N is positive integer, meets 2≤n≤100.
Preferably, A in the formula (I)11Selected from methylene；R01, R02, R03, R04Independently selected from hydrogen, C1~C4In alkyl One kind；R05, R06, R07, R08, R09, R10, R11, R12, R13Independently selected from one of hydrogen, methyl；
R in formula (II)21, R22, R23, R24, R25Independently selected from one of methyl, hydrogen, amino；
R in formula (III)31, R32, R33Independently selected from one of methyl, hydrogen, amino；
R in formula (VI)41, R42Independently selected from one of methyl, hydrogen, amino；
N is positive integer, meets 2≤n≤100.
Preferably, A in the formula (I)11Selected from methylene；R01, R02, R03, R04Independently selected from hydrogen, C1~C2In alkyl One kind；R05, R06, R07, R08, R09, R10, R11, R12, R13Independently selected from one of hydrogen, methyl；
R in formula (II)21, R22, R23, R24, R25For hydrogen；
R in formula (III)31, R32, R33Independently selected from one of hydrogen, amino；
R in formula (VI)41, R42Independently selected from one of hydrogen, amino.
N is positive integer, meets 2≤n≤100.
Preferably, n is positive integer, meets 4≤n≤50.
It is highly preferred that n is positive integer, meet 5≤n≤20.
Preferably, the phosphorus-nitrogen containing polyether polyol is selected from least one of the compound with chemical formula shown in formula (V):
Wherein, n is positive integer, meets 2≤n≤100.
Preferably, the number-average molecular weight of the phosphorus-nitrogen containing polyether polyol is 350~20000Da.
Preferably, the number-average molecular weight of the phosphorus-nitrogen containing polyether polyol is 700~10000Da.
It is further preferred that the number-average molecular weight of the phosphorus-nitrogen containing polyether polyol is 800~5000Da.
The preparation method of the phosphorus-nitrogen containing polyether polyol includes at least following steps:
By containing aldehyde radical functional polyethers polyalcohol, phosphorus-containing compound, containing the raw material of amino-compound, be placed in 70~100 DEG C Reaction 3~30 hours to get；
Wherein, phosphorus-containing compound is selected from least one of the compound containing P-H key.
Preferably, according to mass parts meter, contain in the raw material:
100 mass parts of aldehyde radical functional polyethers polyalcohol；30~150 mass parts of phosphorus-containing compound；Containing amino-compound 10~ 80 mass parts.
Preferably, according to mass parts meter, contain in the raw material:
100 mass parts of aldehyde radical functional polyethers polyalcohol；40~100 mass parts of phosphorus-containing compound；Containing amino-compound 20~ 60 mass parts.
Preferably, according to mass parts meter, contain in the raw material:
100 parts of aldehyde radical functional polyethers polyalcohol；40~120 parts of phosphorus-containing compound；Containing 30~54 parts of amino-compound.
Preferably, the aldehyde radical functional polyethers polyalcohol, which is selected from, has at least one of formula (I-1) compound represented:
Wherein, A11Selected from C1~C3One of alkylidene；
R'11, R'12, R'13, R'14Independently selected from one of hydrogen, alkyl；
N is positive integer, meets 2≤n≤100.
Preferably, A in the formula (I-1)11Selected from C1~C2One of alkylidene；R'11, R'12, R'13, R'14Independently Selected from hydrogen, C1~C4One of alkyl；N is positive integer, meets 2≤n≤100.
Preferably, A in the formula (I-1)11For methylene；R'11, R'12, R'13, R'14Independently selected from hydrogen, methyl It is a kind of；N is positive integer, meets 2≤n≤100.
Preferably, A in the formula (I-1)11For methylene；R'11, R'12, R'13, R'14It is hydrogen；N is positive integer, is met 2≤n≤100。
Preferably, n is positive integer in the formula (I-1), meets 4≤n≤50.
It is highly preferred that n is positive integer in the formula (I-1), meet 5≤n≤20.
Preferably, the number-average molecular weight of the aldehyde radical functional polyethers polyalcohol is 350~20000Da.
Preferably, the number-average molecular weight of the aldehyde radical functional polyethers polyalcohol is 700~10000Da.
Preferably, the number-average molecular weight of the aldehyde radical functional polyethers polyalcohol is 800~5000Da.
Preferably, described to be selected from the chemical combination with structure shown in formula (I-2), formula (I-3), formula (I-4) containing amino-compound At least one of object:
Wherein, R' in formula (I-2)21Selected from C1~C4One of alkyl, hydrogen；R'22, R'23, R'24, R'25, R'26Independently Selected from C1~C4One of alkyl, hydrogen, amino；
R' in formula (I-3)31Selected from C1~C4One of alkyl, hydrogen；R'32, R'33, R'34Independently selected from C1~C4Alkane One of base, hydrogen, amino；
R' in formula (I-4)41Selected from C1~C4One of alkyl, hydrogen；R'42, R'43Independently selected from C1~C4Alkyl, hydrogen, One of amino.
Preferably, R in formula (I-2)21Selected from C1~C2One of alkyl, hydrogen；R'22, R'23, R'24, R'25, R'26It is independent Ground is selected from C1~C2One of alkyl, hydrogen, amino；
R' in formula (I-3)31Selected from C1~C2One of alkyl, hydrogen；R'32, R'33, R'34Independently selected from C1~C2Alkane One of base, hydrogen, amino；
R' in formula (I-4)41Selected from C1~C2One of alkyl, hydrogen；R'42, R'43Independently selected from C1~C2Alkyl, hydrogen, One of amino.
It is highly preferred that R' in formula (I-2)21, R'22, R'23, R'24, R'25, R'26It is hydrogen；
R' in formula (I-3)31, R'32, R'33, R'34It is hydrogen；R' in formula (I-4)41For hydrogen；R'42, R'43For amino.
Preferably, the phosphorus-containing compound is selected from least one of the compound with structure shown in formula (I-5):
Wherein, R'51, R'52, R'53, R'54, R'55, R'56, R'57, R'58Independently selected from C1~C4One in alkyl, hydrogen Kind.
Preferably, R' in formula (I-5)51, R'52, R'53, R'54, R'55, R'56, R'57, R'58It is hydrogen.
Preferably, the aldehyde radical functional polyethers polyalcohol is selected from the compound with structure shown in formula (1-6) at least It is a kind of:
Wherein, n is positive integer, meets 2≤n≤100；
Preferably, n is positive integer in the formula (I-6), meets 3≤n≤50.
Preferably, n is positive integer in the formula (I-6), meets 4≤n≤20.
The phosphorus-containing compound is in the miscellaneous -10- phospho hetero phenanthrene -10- oxide of 9,10- dihydro-9-oxy, dimethylphosphite At least one；
It is described to be selected from least one of aniline, 2- pyrilamine, melamine containing amino-compound.
Preferably, the condition of the reaction is 70~85 DEG C of reactions 5~25 hours；
The solvent of the mixed solution is selected from least one of DMF, DMSO, DMAC, NMP.
As a preferred embodiment, the method includes at least following steps: according to the mass fraction, by 100 parts Aldehyde radical functional polyethers polyalcohol, 30~150 parts of phosphorus-containing compounds, 10~80 parts be dissolved in DMF containing amino-compound, heating reaction It is prepared.
Preferably, the preparation method of aldehyde radical functional polyethers polyalcohol shown in formula (I-1), at least includes the following steps:
(1) by containing the raw material to hydroxyaryl formaldehyde, substituted epoxy compound, under the action of catalyst I, reflux is anti- It answers 1~8 hour, obtains structural formula as shown in formula (I-9) to hydroxyaryl formaldehyde epoxide ether；Wherein, to hydroxyl virtue Base formaldehyde, which is selected from, has at least one of compound shown in formula (I-7):
The substituted epoxy compound, which is selected from, has at least one of compound shown in formula (I-8):
Wherein, R'71, R'72, R'73, R'74Independently selected from one of hydrogen, alkyl；
A18Selected from C1~C3One of alkylidene；X is selected from one of halogen；
(2) under non-active gas atmosphere, resulting structures formula is as shown in formula (I-9) to hydroxyaryl first in step (1) Under the action of catalyst II, 30~120 DEG C are reacted 1~8 hour aldehyde epoxide ether, and it is more to obtain the aldehyde radical functional polyethers First alcohol.
Shown in the structural formula such as formula (I-9) to hydroxyaryl formaldehyde glycidol ether:
Wherein, A19Selected from C1~C3One of alkylidene；
R'91, R'92, R'93, R'94Independently selected from one of hydrogen, alkyl.
Preferably, R' in formula (I-7)71, R'72, R'73, R'74Independently selected from hydrogen, C1~C4One of alkyl；Into one It walks preferably, R'71, R'72, R'73, R'74Independently selected from one of hydrogen, methyl.
Preferably, R' in formula (I-7)71, R'72, R'73, R'74It is hydrogen.
Preferably, A in formula (I-8)18For methylene；X is selected from one of Cl, Br, I.
Preferably, A in formula (I-8)18For methylene；X is Cl.
Preferably, A in formula (I-9)19For methylene；R'91, R'92, R'93, R'94Independently selected from hydrogen, C1~C4In alkyl One kind.It is further preferred that A in formula (I-9)19For methylene；R'91, R'92, R'93, R'94Independently selected from hydrogen, methyl One kind.
Preferably, specific reaction condition in step (1) are as follows: hydroxyaryl formaldehyde, catalyst I, organic solvent will be mixed It closes uniformly, is heated to flowing back in the case where non-active gas protects atmosphere, substituted epoxy compound is then added, back flow reaction obtains Structural formula hydroxyaryl formaldehyde epoxide ether as shown in formula (I-9).
Preferably, it is to the mass ratio of hydroxyaryl formaldehyde, substituted epoxy compound and catalyst I described in step (1) 1:1~5:1~8.
Preferably, it is to the mass ratio of hydroxyaryl formaldehyde, substituted epoxy compound and catalyst I described in step (1) 1:2~4:2~6.
The catalyst I is selected from least one of the carbonate of alkali metal.
Preferably, the carbonate of the alkali metal is selected from least one of Anhydrous potassium carbonate, natrium carbonicum calcinatum.
Preferably, the organic solvent is selected from least one of dehydrated alcohol, tetrahydrofuran, dioxane.
Preferably, organic solvent and the mass ratio to hydroxyaryl formaldehyde are 1:10~50.
Preferably, organic solvent and the mass ratio to hydroxyaryl formaldehyde are 1:20~25.
Preferably, the condition of back flow reaction described in step (1) be 50~90 DEG C back flow reaction 1~3 hour.
It is highly preferred that the condition of back flow reaction described in step (1) be 65~85 DEG C back flow reaction 2 hours.
Preferably, it is 10 to the mass ratio of hydroxyaryl formaldehyde epoxide ether and catalyst II described in step (2): 0.1~10.
Preferably, it is 10 to the mass ratio of hydroxyaryl formaldehyde epoxide ether and catalyst II described in step (2): 0.2~5.
The catalyst II in tetra-n-butyl ammonium acetate, tetra-n-butyl ammonium fluoride, tetra-n-butyl ammonium bromide at least It is a kind of.
Preferably, reaction condition is 50~85 DEG C of reactions 2 hours in step (2).
It is preferably carried out mode as one kind, the method for preparing above-mentioned aldehyde radical functional polyethers polyalcohol includes at least following Step:
A. according to the mass fraction, by 1 part of parahydroxyben-zaldehyde, the carbonate of 1~8 part of alkali metal, 20~50 parts it is organic molten Agent sequentially adds in 500mL four-hole bottle, is uniformly mixed, and leads to nitrogen protection, is heated to flowing back；1~5 part of epoxy chlorine is added dropwise in stirring Propane is then refluxed for reaction 1~8 hour；It obtains after product is purified to hydroxyaryl formaldehyde epoxide ether；
B. according to the mass fraction, three are added to hydroxyaryl formaldehyde epoxide ether, 0.1~10 part of catalyst by 10 parts In mouthful bottle, lead to nitrogen, be stirred to react 1~20 hour, acidic methanol and tetrahydrofuran quenching reaction is added, respectively with n-hexane, It after water sedimentation, is dissolved in acid tetrahydrofuran, is kept for 5 hours, product is washed, dries to obtain aldehyde radical functional polyethers polyalcohol.
Preferably, the flame retardant polyurethane is by pure and mild more containing phosphorus-nitrogen containing polyether polyol, polyether polyol, polyester polyols The raw material of isocyanates is prepared in the presence of a catalyst.
Preferably, by weight, catalyst is 0.1~0.3 parts by weight, and raw material includes:
10~50 parts by weight of phosphorus-nitrogen containing polyether polyol；5~50 parts by weight of polyether polyol；2~50 weight of polyester polyol Measure part；4~100 parts by weight of polyisocyanates.
Preferably, by weight, catalyst is 0.1~0.3 parts by weight, and raw material includes:
10~50 parts by weight of phosphorus-nitrogen containing polyether polyol；10~50 parts by weight of polyether polyol；Polyester polyol 10~50 Parts by weight；5~100 parts by weight of polyisocyanates.
Preferably, by weight, catalyst is 0.1~0.3 parts by weight, and raw material includes:
20 parts by weight of phosphorus-nitrogen containing polyether polyol；5~25 parts by weight of polyether polyol；2.5~20 weight of polyester polyol Part；4.2~6.6 parts by weight of polyisocyanates.
Preferably, the polyether polyol is selected from polyethylene glycol dihydric alcohol, polypropylene glycol diols, polytetrahydrofuran binary At least one of alcohol.
Preferably, the molecular weight of the polyether polyol is 600~5000Da.It is further preferred that the polyether polyols The molecular weight of alcohol is 1000~3000Da.
The polyester polyol is selected from polyethylene glycol adipate dihydric alcohol, poly adipate succinic acid ester dihydric alcohol, gathers oneself At least one of lactone dihydric alcohol, polycarbonate glycol.
Preferably, the molecular weight of the polyester polyol is 600~5000Da.It is further preferred that the polyether polyols The molecular weight of alcohol is 1000~3000Da.
Preferably, the catalyst is selected from least one of organic tin salt.
Preferably, the catalyst is dibutyl tin dilaurate.
The polyisocyanates is selected from toluene di-isocyanate(TDI) (TDI), 1,4- tetramethylene diisocyanate, six Asia 1,6- It is methyl diisocyanate (HDI), ten dimethylene diisocyanate of 1,12-, hexamethylene -1,3- or 1,4- diisocyanate, different Isophorone diisocyanate (IPDI), diphenyl methane 4,4- diisocyanate (MDI), double-hexyl methane diisocyanate (HMDI), 1, hexamethylene-diisocyanate (HDI), polymethylene multi-phenenyl isocyanate (PAPI), phenylenedimethylidyne diisocyanate Ester (XDI), naphthalene -1,5- diisocyanate (NDI), Methylcyclohexyl diisocyanate (HTDI), tetramethylxylene two Isocyanates (TMXDI), hydrogenation methylenebis phenyl isocyanate (H12At least one of MDI).
Preferably, the polyisocyanates is selected from isophorone diisocyanate (IPDI), toluene di-isocyanate(TDI) (TDI), 1,6- hexamethylene diisocyanate (HDI), double-hexyl methane diisocyanate (HMDI), diphenyl methane 4,4- Diisocyanate (MDI), toluene di-isocyanate(TDI) (TDI), hydrogenation methylenebis phenyl isocyanate (H12MDI at least one in) Kind.
The method that above-mentioned flame retardant polyurethane is prepared in the application, at least includes the following steps:
By phosphorus-nitrogen containing polyether polyol, polyether polyol, polyester polyol mix and by dehydration, addition organic solvent, Then catalyst and polyisocyanates is added, 3~5h is reacted under conditions of 60~100 DEG C, obtains flame retardant polyurethane.
Preferably, the mode of the water removal are as follows: be warming up to 100~120 DEG C, vaccum dewatering 1~3 hour.
Preferably, the organic solvent is at least one of DMF, DMSO, DMAC, NMP.
Flame retardant polyurethane in the application by phosphorus-nitrogen containing polyether polyol as additive flame retardant, can be with isocyanic acid Ester occurs chemical reaction and generates carbamate groups, and ignition-proof element phosphorus nitrogen is introduced polyurethane net in the form of covalent bond Network avoids the deficiencies of physical blending additive flame retardant is easily precipitated, migrates.
In the application, the non-active gas protection atmosphere is selected from least one of nitrogen, helium, neon, argon gas.
Aldehyde radical functional polyethers polyalcohol according to the present invention is used to prepare the purposes of polyurethane, the polyurethane, including Polyurethane products known to this fields engineer such as polyurethane elastomer, polyurethane foam and aqueous polyurethane.
Aldehyde radical functional polyethers polyalcohol according to the present invention is used to prepare the purposes of polyurethane, and the polyurethane is answered With field can be related to this fields engineer such as thermal insulation material, encapsulating material, coating, adhesive, leather known to application field.
In the application, " alkyl " refers to the group formed by losing any one hydrogen atom on alkane compound molecule.Alkane Hydrocarbon compound includes cycloalkane, linear paraffin, branched paraffin.
In the application, C1~C2、C1~C4Etc. the carbon atom number for referring both to group and being included.
The beneficial effect that the application can generate includes:
1) it is anti-with isocyanates chemistry can to occur for flame retardant polyurethane provided herein by phosphorus-nitrogen containing polyether polyol Carbamate groups should be generated, ignition-proof element phosphorus nitrogen are introduced into polyurethane network in the form of covalent bond, as addition type Fire retardant is for avoiding the deficiencies of physical blending additive flame retardant is easily precipitated, migrates in flame retardant polyurethane.
2) preparation method of flame retardant polyurethane provided herein is simple, and raw material is easy to get.
3) flame retardant polyurethane provided herein has excellent flame retardant property, anti-hydrolytic performance and mechanical property.
Detailed description of the invention
Fig. 1 is the nuclear magnetic resoance spectrum hydrogen spectrogram of parahydroxyben-zaldehyde glycidol ether in embodiment 1.
Fig. 2 is the nuclear magnetic resoance spectrum hydrogen spectrogram of aldehyde radical functional polyethers polyalcohol in embodiment 1.
Fig. 3 is the synthesis schematic diagram of phosphorus-nitrogen containing polyether polyol in embodiment.
Fig. 4 is the nuclear magnetic resoance spectrum hydrogen spectrogram of the phosphorus-nitrogen containing polyether polyol D1 of embodiment 4.
Fig. 5 is the nuclear magnetic resoance spectrum phosphorus spectrogram of the phosphorus-nitrogen containing polyether polyol D1 of embodiment 4.
Specific embodiment
The application is described in detail below with reference to embodiment, but the application is not limited to these embodiments.
Unless otherwise instructed, the raw material in embodiments herein and catalyst are bought by commercial sources.
Analysis method is as follows in embodiments herein:
Hydrogen nuclear magnetic resonance spectrum analysis is carried out using AVANCE III HD (Bruker-BioSpin) nuclear magnetic resonance spectrometer.
Nuclear magnetic resonance phosphorus spectrum analysis is carried out using AVANCE III HD (Bruker-BioSpin) nuclear magnetic resonance spectrometer.
In the application, polypropylene glycol is abbreviated as PPG, and molecular weight is about 2000Da.
In the application, polyadipate -1,4-butanediol esterdiol PBA, molecular weight is about 2000Da.
The preparation of 1 aldehyde radical functional polyethers polyalcohol C1 of embodiment
The synthesis of a1 parahydroxyben-zaldehyde glycidol ether
One with blender, reflux condensing tube, nitrogen injection pipe 500mL four-necked bottle in be added 6 grams of para hydroxybenzene first Aldehyde, 20.4 grams of Anhydrous potassium carbonates and 144 grams of dehydrated alcohols lead to nitrogen, are heated with stirring to 10.8 grams of rings of dropwise addition in 80 DEG C, 30 minutes Oxygen chloropropane, 80 DEG C back flow reaction two hours；It is filtered to remove potassium carbonate, filtrate decompression distillation, product is dissolved in ethyl acetate, water It washes, organic phase is dry using anhydrous magnesium sulfate, and vacuum distillation crosses column, obtains parahydroxyben-zaldehyde glycidol ether.Its nuclear magnetic resonance It is as shown in Figure 1 to compose hydrogen spectrogram.
The synthesis of b1 aldehyde radical functional polyethers polyalcohol
In the 100mL there-necked flask that one has blender, nitrogen injection pipe, 7.0g parahydroxyben-zaldehyde glycidol is added Ether (obtains) in step a1, leads to nitrogen, and 1.0g tetrabutylammonium acetate ammonium is added, and 55 DEG C are reacted 2 hours；5mL tetrahydrofuran is added, then 20mL acidic methanol (HCl: methanol=1:10) quenching reaction is added, successively uses n-hexane, water sedimentation.It is dissolved in 20mL acidity four Hydrogen furans (HCl: tetrahydrofuran=1:10) stands 2 hours, using water sedimentation, obtains aldehyde radical functional polyethers polyalcohol, be denoted as C1. Its chemical formula is as shown in Formulas I -6, wherein n=12.Nuclear magnetic resoance spectrum hydrogen spectrogram is as shown in Figure 2.
The preparation of 2 aldehyde radical functional polyethers polyalcohol C2 of embodiment
The synthesis of a2 parahydroxyben-zaldehyde glycidol ether
One with blender, reflux condensing tube, nitrogen injection pipe 500mL four-necked bottle in be added 6 grams of para hydroxybenzene first Aldehyde, 28 grams of natrium carbonicum calcinatums and 120 grams of dioxane lead to nitrogen, are heated with stirring to 10.8 grams of epoxies of dropwise addition in 80 DEG C, 30 minutes Chloropropane, 80 DEG C back flow reaction two hours；It is filtered to remove sodium carbonate, filtrate decompression distillation, product is dissolved in ethyl acetate, water It washes, organic phase is dry using anhydrous magnesium sulfate, and vacuum distillation crosses column, obtains parahydroxyben-zaldehyde glycidol ether.
The synthesis of b2 aldehyde radical functional polyethers polyalcohol
In the 100mL there-necked flask that one has blender, nitrogen injection pipe, 7.0g parahydroxyben-zaldehyde glycidol is added Ether (obtains) in step a2, leads to nitrogen, and 0.5g tetrabutyl ammonium fluoride is added, and 80 DEG C are reacted 2 hours；5mL tetrahydrofuran is added, then 20mL acidic methanol (HCl: methanol=1:10) quenching reaction is added, successively uses n-hexane, water sedimentation.It is dissolved in 20mL acidity four Hydrogen furans (HCl: tetrahydrofuran=1:10) stands 2 hours, using water sedimentation, obtains aldehyde radical functional polyethers polyalcohol, be denoted as C2. Its chemical formula is as shown in Formulas I -6, wherein n=20.
The nuclear magnetic resonance of parahydroxyben-zaldehyde glycidol ether obtained in the present embodiment and aldehyde radical functional polyethers polyalcohol Hydrogen spectrogram is identical as the test result in embodiment 1 to get having arrived target product.
The preparation of 3 aldehyde radical functional polyethers polyalcohol C3 of embodiment
The synthesis of a3 parahydroxyben-zaldehyde glycidol ether
One with blender, reflux condensing tube, nitrogen injection pipe 500mL four-necked bottle in be added 6 grams of para hydroxybenzene first Aldehyde, 20.4 grams of Anhydrous potassium carbonates and 150 grams of tetrahydrofurans lead to nitrogen, are heated with stirring to 10.8 grams of rings of dropwise addition in 65 DEG C, 30 minutes Oxygen chloropropane, 65 DEG C back flow reaction two hours；It is filtered to remove potassium carbonate, filtrate decompression distillation, product is dissolved in ethyl acetate, water It washes, organic phase is dry using anhydrous magnesium sulfate, vacuum distillation, crosses column and obtains parahydroxyben-zaldehyde glycidol ether.
The synthesis of b3 aldehyde radical functional polyethers polyalcohol
In the 100mL there-necked flask that one has blender, nitrogen injection pipe, 7.0g parahydroxyben-zaldehyde glycidol is added Ether (obtains) in step a3, leads to nitrogen, and 1.5g tetrabutylammonium acetate ammonium is added, and 90 DEG C are reacted 2 hours；5mL tetrahydrofuran is added, then 20mL acidic methanol (HCl: methanol=1:10) quenching reaction is added, successively uses n-hexane, water sedimentation.It is dissolved in 20mL acidity four Hydrogen furans (HCl: tetrahydrofuran=1:10) stands 2 hours, using water sedimentation, obtains aldehyde radical functional polyethers polyalcohol, be denoted as C3. Its chemical formula is as shown in Formulas I -6, wherein n=8.
The nuclear magnetic resonance of parahydroxyben-zaldehyde glycidol ether obtained in the present embodiment and aldehyde radical functional polyethers polyalcohol Hydrogen spectrogram is identical as the test result in embodiment 1 to get having arrived target product.
The synthesis of 4 phosphorus-nitrogen containing polyether polyol D1 of embodiment
3.0 grams of aldehyde radical functional polyethers polyalcohols, 1.4 grams of benzene are added in a 100mL flask with reflux condensing tube Amine, 3.6 grams of DOPO are added the dry DMF of 50mL, are warming up to 78 DEG C, react 5 hours, obtain phosphorus-nitrogen containing polyether polyol, be denoted as D1.
Wherein, aldehyde radical functional polyethers polyalcohol is C1.
The chemical formula of phosphorus-nitrogen containing polyether polyol D1 obtained by the above method is as shown in figure 4, reaction equation such as Fig. 3 institute Show.
Fig. 4 and Fig. 5 is respectively the hydrogen nuclear magnetic resonance spectrogram and nuclear magnetic resonance for the phosphorus-nitrogen containing polyether polyol D1 being prepared Phosphorus spectrogram.
The synthesis of 5 phosphorus-nitrogen containing polyether polyol D2 of embodiment
3.0 grams of aldehyde radical functional polyethers polyalcohols, 1.6 grams of 2- are added in a 100mL flask with reflux condensing tube Pyrilamine, 3.6 grams of DOPO are added the dry DMF of 50mL, are warming up to 80 DEG C, react 20 hours, obtain phosphorus-nitrogen containing polyether polyol, remember For D2.
Wherein, aldehyde radical functional polyethers polyalcohol is C2.
The synthesis of 6 phosphorus-nitrogen containing polyether polyol D3 of embodiment
3.0 grams of aldehyde radical functional polyethers polyalcohols of addition in a 100mL flask with reflux condensing tube, 0.6 gram three Poly cyanamid, 1.2 grams of dimethylphosphites are added the dry DMF of 50mL, are warming up to 78 DEG C, react 25 hours, it is more to obtain phosphorus-nitrogen containing polyethers First alcohol, is denoted as D3.
Wherein, aldehyde radical functional polyethers polyalcohol is C3.
The synthesis of 7 phosphorus-nitrogen containing polyether polyol D4 of embodiment
3.0 grams of aldehyde radical functional polyethers polyalcohols of addition in a 100mL flask with reflux condensing tube, 0.6 gram three Poly cyanamid, 1.2 grams of dimethylphosphites are added the dry DMF of 50mL, are warming up to 85 DEG C, react 15 hours, it is more to obtain phosphorus-nitrogen containing polyethers First alcohol, is denoted as D4.
Wherein, aldehyde radical functional polyethers polyalcohol is C1.
The preparation of 8 flame retardant polyurethane J1 of embodiment
20.0 grams of response type phosphorus-nitrogen containing polyether polyol (D1) of addition into reactor, 10.0 grams of PPG2000,20.0 grams PBA2000 is heated to 110 DEG C, vaccum dewatering 2 hours, 50.0mL DMF is added, and after dissolution, the drop of 5.6 grams of IPDI and 4 two is added Butyl tin dilaurate tin reacts 4 hours at 80 DEG C, obtains phosphorus nitrogen synergetic flame-retardant polyurethane, be denoted as J1.
The preparation of 9 flame retardant polyurethane J2 of embodiment
20.0 grams of response type phosphorus-nitrogen containing polyether polyol (D2) of addition into reactor, 5.0 grams of PPG2000,25.0 grams PBA2000 is heated to 110 DEG C, vaccum dewatering 2 hours, 50.0mL DMF is added, and after dissolution, 4.2 grams of HDI and 4, two fourths of drop are added Base tin dilaurate tin reacts 4 hours at 75 DEG C, obtains phosphorus nitrogen synergetic flame-retardant polyurethane, be denoted as J2.
The preparation of 10 flame retardant polyurethane J3 of embodiment
20.0 grams of response type phosphorus-nitrogen containing polyether polyol (D3) of addition into reactor, 25.0 grams of PPG2000,5.0 grams PBA2000 is heated to 110 DEG C, vaccum dewatering 2 hours, 50.0mL DMF is added, and after dissolution, 5.2 grams of MDI and 4, two fourths of drop are added Base tin dilaurate tin reacts 4 hours at 85 DEG C, obtains phosphorus nitrogen synergetic flame-retardant polyurethane, be denoted as J3.
The preparation of 11 flame retardant polyurethane J4 of embodiment
20.0 grams of response type phosphorus-nitrogen containing polyether polyol (D4) of addition into reactor, 20.0 grams of PPG2000,10.0 grams PBA2000 is heated to 110 DEG C, vaccum dewatering 2 hours, 50.0mL DMF is added, after dissolution, 5.4 grams of H are added12The drop of MDI and 4 two Butyl tin dilaurate tin reacts 4 hours at 90 DEG C, obtains phosphorus nitrogen synergetic flame-retardant polyurethane, be denoted as J4.
The test of 12 flame retardant property of embodiment
According to the method in GB/T 2408-2008 standard (combustion testing standard) to the flame retardant property of sample J1~J4 into Row measurement, the results are shown in Table 1.
Table 1
From table 1 it follows that the flame retardant polyurethane J1~J4 being prepared has excellent flame retardant effect.
13 Mechanics Performance Testing of embodiment
Mechanics Performance Testing is carried out to sample J1~J4；Wherein, the measurement of tensile property is according to side in GB/T13022-91 Method measurement.Test result is as shown in table 2.
Table 2
From Table 2, it can be seen that the flame retardant polyurethane J1~J4 being prepared has excellent mechanical property.
The above is only several embodiments of the application, not does any type of limitation to the application, although this Shen Please disclosed as above with preferred embodiment, however not to limit the application, any person skilled in the art is not taking off In the range of technical scheme, a little variation or modification are made using the technology contents of the disclosure above and is equal to Case study on implementation is imitated, is belonged in technical proposal scope.

Claims (10)

1. a kind of flame retardant polyurethane, which is characterized in that be prepared by the raw material containing phosphorus-nitrogen containing polyether polyol；
The phosphorus-nitrogen containing polyether polyol is selected from least one of the compound with the chemical formula as shown in formula (I):
Wherein, A00Selected from C1~C3One of alkylidene；
R01, R02, R03, R04Independently selected from one of hydrogen, alkyl；
R05, R06, R07, R08, R09, R10, R11, R12, R13Independently selected from hydrogen, C1~C4One of alkyl；
R14Selected from one of group shown in formula (II), formula (III), formula (IV):
R in formula (II)21, R22, R23, R24, R25Independently selected from C1~C4Alkyl, C1~C4Replace alkyl, hydrogen, one in amino Kind；
R in formula (III)31, R32, R33Independently selected from C1~C4One of alkyl, hydrogen, amino；
R in formula (IV)41, R42Independently selected from C1~C4One of alkyl, hydrogen, amino；
N is positive integer, meets 2≤n≤100.
2. flame retardant polyurethane according to claim 1, which is characterized in that the phosphorus-nitrogen containing polyether polyol, which is selected from, to be had such as At least one of the compound of chemical formula shown in formula (V):
Wherein, n is positive integer, meets 2≤n≤100.
3. flame retardant polyurethane according to claim 2, which is characterized in that the equal molecule of number of the phosphorus-nitrogen containing polyether polyol Amount is 350~20000Da.
4. flame retardant polyurethane according to claim 1, which is characterized in that by more containing phosphorus-nitrogen containing polyether polyol, polyethers The raw material of the pure and mild polyisocyanates of first alcohol, polyester polyols is prepared in the presence of a catalyst.
5. flame retardant polyurethane according to claim 4, which is characterized in that by weight, catalyst is 0.1~0.3 weight Part is measured, raw material includes:
10~50 parts by weight of phosphorus-nitrogen containing polyether polyol；
5~50 parts by weight of polyether polyol；
2~50 parts by weight of polyester polyol；
4~100 parts by weight of polyisocyanates.
6. flame retardant polyurethane according to claim 4, which is characterized in that by weight, catalyst is 0.1~0.3 weight Part is measured, raw material includes:
10~50 parts by weight of phosphorus-nitrogen containing polyether polyol；
10~50 parts by weight of polyether polyol；
10~50 parts by weight of polyester polyol；
5~100 parts by weight of polyisocyanates.
7. flame retardant polyurethane according to claim 4, which is characterized in that by weight, catalyst is 0.1~0.3 weight Part is measured, raw material includes:
20 parts by weight of phosphorus-nitrogen containing polyether polyol；
5~25 parts by weight of polyether polyol；
2.5~20 parts by weight of polyester polyol；
4.2~6.6 parts by weight of polyisocyanates.
8. according to the described in any item flame retardant polyurethanes of claim 4 to 7, which is characterized in that the polyether polyol is selected from poly- At least one of ethylene glycol dihydric alcohol, polypropylene glycol diols, polytetrahydrofuran dihydric alcohol；
The polyester polyol is selected from polyethylene glycol adipate dihydric alcohol, poly adipate succinic acid ester dihydric alcohol, polycaprolactone At least one of dihydric alcohol, polycarbonate glycol；
The catalyst is selected from least one of organic tin salt；
It is different that the polyisocyanates is selected from toluene di-isocyanate(TDI), 1,4- tetramethylene diisocyanate, 1,6- hexa-methylene two Cyanate, ten dimethylene diisocyanate of 1,12-, hexamethylene -1,3- diisocyanate, hexamethylene -1,4- diisocyanate, Isophorone diisocyanate, diphenyl methane 4,4- diisocyanate, double-hexyl methane diisocyanate, polymethylene are more Phenyl isocyanate, benzene dimethylene diisocyanate, naphthalene -1,5- diisocyanate, Methylcyclohexyl diisocyanate, tetramethyl At least one of base benzene dimethylene diisocyanate, hydrogenation methylenebis phenyl isocyanate.
9. the method for preparing the described in any item flame retardant polyurethanes of claim 4 to 8, which is characterized in that include at least following step It is rapid:
By phosphorus-nitrogen containing polyether polyol, polyether polyol, polyester polyol mix and by dehydration, addition organic solvent, then Catalyst and polyisocyanates is added, 3~5h is reacted under conditions of 70~100 DEG C, obtains flame retardant polyurethane.
10. according to the method described in claim 9, it is characterized in that, the mode of the water removal are as follows: 100~120 DEG C are warming up to, Vaccum dewatering 1~3 hour.
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