CN107686547A - flame retardant polyurethane and preparation method thereof - Google Patents
flame retardant polyurethane and preparation method thereof Download PDFInfo
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- CN107686547A CN107686547A CN201710917397.4A CN201710917397A CN107686547A CN 107686547 A CN107686547 A CN 107686547A CN 201710917397 A CN201710917397 A CN 201710917397A CN 107686547 A CN107686547 A CN 107686547A
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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
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- 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
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- 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
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- 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
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- 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
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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
- 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
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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
- 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
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- C—CHEMISTRY; METALLURGY
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- 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
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Abstract
This application discloses a kind of flame retardant polyurethane, and it is prepared by the raw material containing phosphorus-nitrogen containing PPG；Ignition-proof element phosphorus nitrogen introduces polyurethane network in the form of covalent bond in the flame retardant polyurethane, is used for as additive flame retardant in flame retardant polyurethane, avoids the deficiencies of physical blending additive flame retardant is easily separated out, migrated.
Description
Technical field
The application is related to a kind of flame retardant polyurethane and preparation method thereof, belongs to fire proofing field.
Background technology
Polyurethane is the high polymer formed by polyisocyanates and polymerization, is a kind of important high polymer material；
In intramolecular and intermolecular while there is highly polar carbamate groups and hydrogen bond, there is high intensity, wear-resisting, pliability
The excellent properties such as good, adhesive force is strong, film-forming temperature is low, solvent resistant；Simultaneously by change the species of polyol, structure,
Molecular weight etc., it can also be widely used in industrial and daily in the interior performance for being conveniently adjusted polyurethane material in a big way
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 physical culture, medical treatment.
Because polyurethane material has incendive hydrocarbon segment in structure, easy burning and difficult self-extinguishment when meeting fiery, combustion
Substantial amounts of flue dust and toxic gas are produced during burning, health and environment peace can also be jeopardized by being brought to fire extinguishing while difficulty
Entirely.Therefore, want to be more widely applied polyurethane material, suitable component and dosage must be just 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
Separate out.The A of Chinese patent CN 106117600 disclose a kind of reactive flame retardant THPP, and there is the fire retardant preferable phosphorus to contain
Amount and carbon left, there is the characteristics such as flame retarding efficiency height and Halogen, low cigarette, low toxicity, durability.The A of Chinese patent CN 104448202
A kind of phosphor-containing flame-proof method for preparing thermoplastic polyurethane elastomer is disclosed, the disclosure technology is using molecular weight as 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 brings up to 32 by 19, and fire resistance is good.
Because hydrolysis easily occurs for the ester bond in polyester, cause to be owed as the polyurethane water resistance obtained by PEPA
It is good.In many application fields, for polyurethane, it is often necessary to this class feature.For example, for can be by PPG system
Standby polyurethane, it is desirable to assign its excellent anti-hydrolytic performance, prepared as the B of Chinese patent CN 103703052 disclose one kind
The method of polyether carbonate polyol, the polyether carbonate polyol as made from the technology have excellent applied to polyurethane field
Performance.Wherein in the first step, by one or more H- functions 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, it is different with least two
Alkylene oxide mixture in the presence of at least one DMC- catalyst to polyether carbonate polyol carry out chain.It is and for example Chinese
The B of patent CN 103314031 disclose 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, during polyurethane products use, easily occurs fire retardant
The defects of separating out, migrating.The A of Chinese patent CN 106496505 disclose the dihydric alcohol preparation 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.The A of Chinese patent CN 106496507 are disclosed with one kind
The dihydric alcohol of phosphorus-nitrogen containing ignition-proof element prepares a kind of method of the RPUF of phosphorus nitrogen cooperative flame retardant.Avoiding makes
With the deficiency of additive flame retardant of the tradition in a manner of physical blending, formed and force compatible, cooperative flame retardant polyurethane foam
Plastics.
The content of the invention
According to the one side of the application, there is provided a kind of flame retardant polyurethane, it is easy to which overcome fire retardant in the prior art
The problem of separating out, migrating, has excellent fire resistance.
The flame retardant polyurethane, it is prepared by the raw material containing phosphorus-nitrogen containing PPG；
The phosphorus-nitrogen containing PPG, which is selected from, has at least one of compound of chemical formula as shown in formula (I)：
Wherein, A00Selected from C1~C3One kind in alkylidene；
R01, R02, R03, R04One kind in hydrogen, alkyl；
R05, R06, R07, R08, R09, R10, R11, R12, R13Independently selected from hydrogen, C1~C4One kind in alkyl；
R14One kind in group shown in formula (II), formula (III), formula (IV)：
R in formula (II)21, R22, R23, R24, R25Independently selected from C1~C4One kind in alkyl, hydrogen, amino；
R in formula (III)31, R32, R33Independently selected from C1~C4One kind in alkyl, hydrogen, amino；
R in formula (IV)41, R42Independently selected from C1~C4One kind in 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, R13One kind in hydrogen, methyl；
R in formula (II)21, R22, R23, R24, R25One kind in methyl, hydrogen, amino；
R in formula (III)31, R32, R33One kind in methyl, hydrogen, amino；
R in formula (VI)41, R42One kind in 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, R13One kind in hydrogen, methyl；
R in formula (II)21, R22, R23, R24, R25For hydrogen；
R in formula (III)31, R32, R33One kind in hydrogen, amino；
R in formula (VI)41, R42One kind in 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 PPG, which is selected from, has at least one of compound of 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 PPG is 350~20000Da.
Preferably, the number-average molecular weight of the phosphorus-nitrogen containing PPG is 700~10000Da.
It is further preferred that the number-average molecular weight of the phosphorus-nitrogen containing PPG is 800~5000Da.
The preparation method of the phosphorus-nitrogen containing PPG, including at least following steps：
By containing aldehyde radical functional polyethers polyalcohol, phosphorus-containing compound, the raw material containing amino-compound, 70~100 DEG C are placed in
Reaction 3~30 hours, is produced；
Wherein, phosphorus-containing compound is selected from least one of compound containing P-H keys.
Preferably, according to mass parts meter, contain in the raw material：
The mass parts of aldehyde radical functional polyethers polyalcohol 100；The mass parts of phosphorus-containing compound 30~150；Containing amino-compound 10~
80 mass parts.
Preferably, according to mass parts meter, contain in the raw material：
The mass parts of aldehyde radical functional polyethers polyalcohol 100；The mass parts of phosphorus-containing compound 40~100；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 is selected from at least one of compound shown in formula (I-1)：
Wherein, A11Selected from C1~C3One kind in alkylidene；
R'11, R'12, R'13, R'14One kind in hydrogen, alkyl；
N is positive integer, meets 2≤n≤100.
Preferably, A in the formula (I-1)11Selected from C1~C2One kind in alkylidene；R'11, R'12, R'13, R'14Independently
Selected from hydrogen, C1~C4One kind in 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'14In 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, it is 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 thing：
Wherein, R' in formula (I-2)21Selected from C1~C4One kind in alkyl, hydrogen；R'22, R'23, R'24, R'25, R'26Independently
Selected from C1~C4One kind in alkyl, hydrogen, amino；
R' in formula (I-3)31Selected from C1~C4One kind in alkyl, hydrogen；R'32, R'33, R'34Independently selected from C1~C4Alkane
One kind in base, hydrogen, amino；
R' in formula (I-4)41Selected from C1~C4One kind in alkyl, hydrogen；R'42, R'43Independently selected from C1~C4Alkyl, hydrogen,
One kind in amino.
Preferably, R in formula (I-2)21Selected from C1~C2One kind in alkyl, hydrogen；R'22, R'23, R'24, R'25, R'26It is independent
Ground is selected from C1~C2One kind in alkyl, hydrogen, amino；
R' in formula (I-3)31Selected from C1~C2One kind in alkyl, hydrogen；R'32, R'33, R'34Independently selected from C1~C2Alkane
One kind in base, hydrogen, amino；
R' in formula (I-4)41Selected from C1~C2One kind in alkyl, hydrogen；R'42, R'43Independently selected from C1~C2Alkyl, hydrogen,
One kind in 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, which is selected from, has at least one of compound of 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, which is selected from, has in the compound of 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 phenanthrenes -10- oxides of 9,10- dihydro-9-oxies, dimethylphosphite
At least one；
It is described to be selected from least one of aniline, 2- pyrilamines, melamine containing amino-compound.
Preferably, the condition of the reaction is reacted 5~25 hours for 70~85 DEG C；
The solvent of the mixed solution is selected from least one of DMF, DMSO, DMAC, NMP.
As a preferred embodiment, methods described comprises 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 containing amino-compound in DMF, heating response
It is prepared.
Preferably, the preparation method of aldehyde radical functional polyethers polyalcohol shown in formula (I-1), including at least following steps：
(1) by containing the raw material to hydroxyaryl formaldehyde, substituted epoxy compound, in the presence of catalyst I, backflow is anti-
Answer 1~8 hour, obtain 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'74One kind in hydrogen, alkyl；
A18Selected from C1~C3One kind in alkylidene；The one kind of X in halogen；
(2) under non-active gas atmosphere, in step (1) resulting structures formula as shown in formula (I-9) to hydroxyaryl first
In the presence 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 kind in alkylidene；
R'91, R'92, R'93, R'94One kind in hydrogen, alkyl.
Preferably, R' in formula (I-7)71, R'72, R'73, R'74Independently selected from hydrogen, C1~C4One kind in alkyl；Enter one
Walk preferably, R'71, R'72, R'73, R'74One kind in 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；The one kind of X in 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'94In hydrogen, methyl
One kind.
Preferably, specific reaction condition is in step (1)：Hydroxyaryl formaldehyde, catalyst I, organic solvent will be mixed
Close uniformly, be heated to flowing back in the case where non-active gas protect atmosphere, then add substituted epoxy compound, back flow reaction, obtain
Hydroxyaryl formaldehyde epoxide ether of the structural formula 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 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 absolute ethyl alcohol, tetrahydrofuran, dioxane.
Preferably, organic solvent is with being 1 to the mass ratio of hydroxyaryl formaldehyde：10~50.
Preferably, organic solvent is with being 1 to the mass ratio of hydroxyaryl formaldehyde：20~25.
Preferably, the condition of back flow reaction described in step (1) is 50~90 DEG C of back flow reactions 1~3 hour.
It is highly preferred that the condition of back flow reaction described in step (1) is 65~85 DEG C of back flow reactions 2 hours.
Preferably, it is 10 to hydroxyaryl formaldehyde epoxide ether and catalyst II mass ratio described in step (2)：
0.1~10.
Preferably, it is 10 to hydroxyaryl formaldehyde epoxide ether and catalyst II mass ratio 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 reacts 2 hours for 50~85 DEG C in step (2).
Mode is preferably carried out as one kind, the method for preparing above-mentioned aldehyde radical functional polyethers polyalcohol, including 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 is sequentially added in 500mL four-hole bottles, is well mixed, and is led to nitrogen protection, is heated to flowing back；Stirring, 1~5 part of epoxy chlorine is added dropwise
Propane, it is then refluxed for reaction 1~8 hour；Must be to hydroxyaryl formaldehyde epoxide ether after product is purified；
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, stirring reaction 1~20 hour, adds acidic methanol and reaction is quenched in tetrahydrofuran, respectively with n-hexane,
After water sedimentation, it is dissolved in acid tetrahydrofuran, is kept for 5 hours, product is through washing, dry aldehyde radical functional polyethers polyalcohol.
Preferably, the flame retardant polyurethane is by containing phosphorus-nitrogen containing PPG, PPG, PEPA and more
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：
The parts by weight of phosphorus-nitrogen containing PPG 10~50；The parts by weight of PPG 5~50；The weight of PEPA 2~50
Measure part；The parts by weight of polyisocyanates 4~100.
Preferably, by weight, catalyst is 0.1~0.3 parts by weight, and raw material includes：
The parts by weight of phosphorus-nitrogen containing PPG 10~50；The parts by weight of PPG 10~50；PEPA 10~50
Parts by weight；The parts by weight of polyisocyanates 5~100.
Preferably, by weight, catalyst is 0.1~0.3 parts by weight, and raw material includes：
The parts by weight of phosphorus-nitrogen containing PPG 20；The parts by weight of PPG 5~25；The weight of PEPA 2.5~20
Part；The parts by weight of polyisocyanates 4.2~6.6.
Preferably, the PPG is selected from polyethylene glycol dihydric alcohol, polypropylene glycol diols, PolyTHF binary
At least one of alcohol.
Preferably, the molecular weight of the PPG is 600~5000Da.It is further preferred that the polyether polyols
The molecular weight of alcohol is 1000~3000Da.
The PEPA is selected from polyethylene glycol adipate dihydric alcohol, poly adipate succinic acid ester dihydric alcohol, gathers oneself
At least one of lactone dihydric alcohol, PCDL.
Preferably, the molecular weight of the PEPA 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.
It is sub- that the polyisocyanates is selected from toluene di-isocyanate(TDI) (TDI), 1,4- tetramethylene diisocyanates, 1,6- six
It is methyl diisocyanate (HDI), the dimethylene diisocyanates of 1,12- ten, 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), the isocyanic acid of phenylenedimethylidyne two
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 IPDI (IPDI), toluene di-isocyanate(TDI)
(TDI), 1,6- hexamethylene diisocyanates (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, including at least following steps：
Phosphorus-nitrogen containing PPG, PPG, PEPA are mixed and by dehydration, add organic solvent,
Then catalyst and polyisocyanates are added, 3~5h is reacted under conditions of 60~100 DEG C, obtains flame retardant polyurethane.
Preferably, the mode of the water removal is：100~120 DEG C are warming up to, vaccum dewatering 1~3 hour.
Preferably, the organic solvent is at least one of DMF, DMSO, DMAC, NMP.
For flame retardant polyurethane in the application by phosphorus-nitrogen containing PPG as additive flame retardant, it can be with isocyanic acid
Chemical reaction generation carbamate groups occur for ester, and ignition-proof element phosphorus nitrogen is introduced into polyurethane net in the form of covalent bond
Network, avoid the deficiencies of physical blending additive flame retardant is easily separated out, migrated.
In the application, the non-active gas protection atmosphere is selected from least one of nitrogen, helium, neon, argon gas.
It is used to preparing the purposes of polyurethane according to the aldehyde radical functional polyethers polyalcohol of the present invention, described polyurethane, including
Polyurethane products known to this area engineer such as polyurethane elastomer, polyurethane foam and aqueous polyurethane.
It is used for the purposes for preparing polyurethane according to the aldehyde radical functional polyethers polyalcohol of the present invention, described polyurethane, it should
The application field known to field can relate to this area engineer such as insulation material, encapsulating material, coating, adhesive, leather.
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 number for referring both to group and being included.
Beneficial effect caused by the application energy includes：
1) flame retardant polyurethane provided herein, it is anti-that chemistry can be occurred with isocyanates by phosphorus-nitrogen containing PPG
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 used in flame retardant polyurethane, avoids the deficiencies of physical blending additive flame retardant is easily separated out, migrated.
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 fire resistance, anti-hydrolytic performance and mechanical property.
Brief description of the drawings
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 PPG in embodiment.
Fig. 4 is the phosphorus-nitrogen containing PPG D1 of embodiment 4 nuclear magnetic resoance spectrum hydrogen spectrogram.
Fig. 5 is the phosphorus-nitrogen containing PPG D1 of embodiment 4 nuclear magnetic resoance spectrum phosphorus spectrogram.
Embodiment
The application is described in detail 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：
Proton nmr spectra analysis is carried out using AVANCE III HD (Bruker-BioSpin) nuclear magnetic resonance spectrometer.
The spectrum analysis of nuclear magnetic resonance phosphorus 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-BDO esterdiol PBA, molecular weight is about 2000Da.
The aldehyde radical functional polyethers polyalcohol C1 of embodiment 1 preparation
The synthesis of a1 parahydroxyben-zaldehyde glycidol ethers
6 grams of para hydroxybenzene first are added in the 500mL four-necked bottles that one carries agitator, reflux condensing tube, nitrogen ascending pipe
Aldehyde, 20.4 grams of Anhydrous potassium carbonates and 144 grams of absolute ethyl alcohols, lead to nitrogen, be heated with stirring to 10.8 grams of rings of dropwise addition in 80 DEG C, 30 minutes
Oxygen chloropropane, 80 DEG C of back flow reactions two hours；Potassium carbonate, filtrate decompression distillation are filtered to remove, product is dissolved in ethyl acetate, water
Wash, organic phase is dried using anhydrous magnesium sulfate, is evaporated under reduced pressure, and is crossed post, is obtained 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 polyalcohols
In the 100mL there-necked flasks that one carries agitator, nitrogen ascending pipe, 7.0g parahydroxyben-zaldehyde glycidols are added
Ether (is obtained) in step a1, leads to nitrogen, adds 1.0g tetrabutylammonium acetate ammoniums, and 55 DEG C are reacted 2 hours；5mL tetrahydrofurans are added, then
Add 20mL acidic methanols (HCl:Methanol=1:10) quenching reaction, successively using n-hexane, water sedimentation.It is dissolved in 20mL acidity four
Hydrogen furans (HCl:Tetrahydrofuran=1:10) 2 hours, are stood, using water sedimentation, aldehyde radical functional polyethers polyalcohol is obtained, is designated as C1.
Its chemical formula as shown in Formulas I -6, wherein, n=12.Nuclear magnetic resoance spectrum hydrogen spectrogram is as shown in Figure 2.
The aldehyde radical functional polyethers polyalcohol C2 of embodiment 2 preparation
The synthesis of a2 parahydroxyben-zaldehyde glycidol ethers
6 grams of para hydroxybenzene first are added in the 500mL four-necked bottles that one carries agitator, reflux condensing tube, nitrogen ascending pipe
Aldehyde, 28 grams of natrium carbonicum calcinatums and 120 grams of dioxane, lead to nitrogen, be heated with stirring to 10.8 grams of epoxies of dropwise addition in 80 DEG C, 30 minutes
Chloropropane, 80 DEG C of back flow reactions two hours；Sodium carbonate, filtrate decompression distillation are filtered to remove, product is dissolved in ethyl acetate, water
Wash, organic phase is dried using anhydrous magnesium sulfate, is evaporated under reduced pressure, and is crossed post, is obtained parahydroxyben-zaldehyde glycidol ether.
The synthesis of b2 aldehyde radical functional polyethers polyalcohols
In the 100mL there-necked flasks that one carries agitator, nitrogen ascending pipe, 7.0g parahydroxyben-zaldehyde glycidols are added
Ether (is obtained) in step a2, leads to nitrogen, adds 0.5g tetrabutyl ammonium fluorides, and 80 DEG C are reacted 2 hours；5mL tetrahydrofurans are added, then
Add 20mL acidic methanols (HCl:Methanol=1:10) quenching reaction, successively using n-hexane, water sedimentation.It is dissolved in 20mL acidity four
Hydrogen furans (HCl:Tetrahydrofuran=1:10) 2 hours, are stood, using water sedimentation, aldehyde radical functional polyethers polyalcohol is obtained, is designated as C2.
Its chemical formula as shown in Formulas I -6, wherein, n=20.
The parahydroxyben-zaldehyde glycidol ether and the nuclear magnetic resonance of aldehyde radical functional polyethers polyalcohol obtained in the present embodiment
Hydrogen spectrogram is identical with the test result in embodiment 1, that is, has obtained target product.
The aldehyde radical functional polyethers polyalcohol C3 of embodiment 3 preparation
The synthesis of a3 parahydroxyben-zaldehyde glycidol ethers
6 grams of para hydroxybenzene first are added in the 500mL four-necked bottles that one carries agitator, reflux condensing tube, nitrogen ascending pipe
Aldehyde, 20.4 grams of Anhydrous potassium carbonates and 150 grams of tetrahydrofurans, lead to nitrogen, be heated with stirring to 10.8 grams of rings of dropwise addition in 65 DEG C, 30 minutes
Oxygen chloropropane, 65 DEG C of back flow reactions two hours；Potassium carbonate, filtrate decompression distillation are filtered to remove, product is dissolved in ethyl acetate, water
Wash, organic phase is dried using anhydrous magnesium sulfate, is evaporated under reduced pressure, and is crossed post and is obtained parahydroxyben-zaldehyde glycidol ether.
The synthesis of b3 aldehyde radical functional polyethers polyalcohols
In the 100mL there-necked flasks that one carries agitator, nitrogen ascending pipe, 7.0g parahydroxyben-zaldehyde glycidols are added
Ether (is obtained) in step a3, leads to nitrogen, adds 1.5g tetrabutylammonium acetate ammoniums, and 90 DEG C are reacted 2 hours；5mL tetrahydrofurans are added, then
Add 20mL acidic methanols (HCl:Methanol=1:10) quenching reaction, successively using n-hexane, water sedimentation.It is dissolved in 20mL acidity four
Hydrogen furans (HCl:Tetrahydrofuran=1:10) 2 hours, are stood, using water sedimentation, aldehyde radical functional polyethers polyalcohol is obtained, is designated as C3.
Its chemical formula as shown in Formulas I -6, wherein, n=8.
The parahydroxyben-zaldehyde glycidol ether and the nuclear magnetic resonance of aldehyde radical functional polyethers polyalcohol obtained in the present embodiment
Hydrogen spectrogram is identical with the test result in embodiment 1, that is, has obtained target product.
The phosphorus-nitrogen containing PPG D1 of embodiment 4 synthesis
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, add 50mL and dry DMF, be warming up to 78 DEG C, react 5 hours, obtain phosphorus-nitrogen containing PPG, be designated as D1.
Wherein, aldehyde radical functional polyethers polyalcohol is C1.
The chemical formula for the phosphorus-nitrogen containing PPG D1 that the above method obtains is as shown in figure 4, reaction equation such as Fig. 3 institutes
Show.
Fig. 4 and Fig. 5 is respectively the hydrogen nuclear magnetic resonance spectrogram and nuclear magnetic resonance for the phosphorus-nitrogen containing PPG D1 being prepared
Phosphorus spectrogram.
The phosphorus-nitrogen containing PPG D2 of embodiment 5 synthesis
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, add 50mL and dry DMF, be warming up to 80 DEG C, react 20 hours, obtain phosphorus-nitrogen containing PPG, remember
For D2.
Wherein, aldehyde radical functional polyethers polyalcohol is C2.
The phosphorus-nitrogen containing PPG D3 of embodiment 6 synthesis
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, add 50mL and dry DMF, be warming up to 78 DEG C, react 25 hours, it is more to obtain phosphorus-nitrogen containing polyethers
First alcohol, is designated as D3.
Wherein, aldehyde radical functional polyethers polyalcohol is C3.
The phosphorus-nitrogen containing PPG D4 of embodiment 7 synthesis
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, add 50mL and dry DMF, be warming up to 85 DEG C, react 15 hours, it is more to obtain phosphorus-nitrogen containing polyethers
First alcohol, is designated as D4.
Wherein, aldehyde radical functional polyethers polyalcohol is C1.
The flame retardant polyurethane J1 of embodiment 8 preparation
20.0 grams of response type phosphorus-nitrogen containing PPGs (D1) of addition into reactor, 10.0 grams of PPG2000,20.0 grams
PBA2000,110 DEG C are heated to, vaccum dewatering 2 hours, adds 50.0mL DMF, after dissolving, add the drops of 5.6 grams of IPDI and 4 two
Butyl tin dilaurate tin, reacted 4 hours at 80 DEG C, obtain phosphorus nitrogen synergetic flame-retardant polyurethane, be designated as J1.
The flame retardant polyurethane J2 of embodiment 9 preparation
20.0 grams of response type phosphorus-nitrogen containing PPGs (D2) of addition into reactor, 5.0 grams of PPG2000,25.0 grams
PBA2000,110 DEG C are heated to, vaccum dewatering 2 hours, adds 50.0mL DMF, after dissolving, add 4.2 grams of HDI and 4, two fourths of drop
Base tin dilaurate tin, reacted 4 hours at 75 DEG C, obtain phosphorus nitrogen synergetic flame-retardant polyurethane, be designated as J2.
The flame retardant polyurethane J3 of embodiment 10 preparation
20.0 grams of response type phosphorus-nitrogen containing PPGs (D3) of addition into reactor, 25.0 grams of PPG2000,5.0 grams
PBA2000,110 DEG C are heated to, vaccum dewatering 2 hours, adds 50.0mL DMF, after dissolving, add 5.2 grams of MDI and 4, two fourths of drop
Base tin dilaurate tin, reacted 4 hours at 85 DEG C, obtain phosphorus nitrogen synergetic flame-retardant polyurethane, be designated as J3.
The flame retardant polyurethane J4 of embodiment 11 preparation
20.0 grams of response type phosphorus-nitrogen containing PPGs (D4) of addition into reactor, 20.0 grams of PPG2000,10.0 grams
PBA2000,110 DEG C are heated to, vaccum dewatering 2 hours, adds 50.0mL DMF, after dissolving, add 5.4 grams of H12The drops of MDI and 4 two
Butyl tin dilaurate tin, reacted 4 hours at 90 DEG C, obtain phosphorus nitrogen synergetic flame-retardant polyurethane, be designated as J4.
The fire resistance of embodiment 12 is tested
Sample J1~J4 fire resistance is entered according to the method in GB/T 2408-2008 standards (combustion testing standard)
Row measure, as a result as 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.
The Mechanics Performance Testing of embodiment 13
Mechanics Performance Testing is carried out to sample J1~J4；Wherein, the measure of tensile property is according to side in GB/T13022-91
Method determines.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.
It is described above, only it is several embodiments of the application, any type of limitation is not done to the application, although this Shen
Please with preferred embodiment disclose as above, but and be not used to limit the application, any person skilled in the art, do not taking off
In the range of technical scheme, make a little variation using the technology contents of the disclosure above or modification is equal to
Case study on implementation is imitated, is belonged in the range of technical scheme.
Claims (10)
1. a kind of flame retardant polyurethane, it is characterised in that be prepared by the raw material containing phosphorus-nitrogen containing PPG；
The phosphorus-nitrogen containing PPG, which is selected from, has at least one of compound of chemical formula as shown in formula (I)：
Wherein, A00Selected from C1~C3One kind in alkylidene；
R01, R02, R03, R04One kind in hydrogen, alkyl；
R05, R06, R07, R08, R09, R10, R11, R12, R13Independently selected from hydrogen, C1~C4One kind in alkyl；
R14One kind in group shown in formula (II), formula (III), formula (IV)：
R in formula (II)21, R22, R23, R24, R25Independently selected from C1~C4Alkyl, C1~C4Substitute one in alkyl, hydrogen, amino
Kind；
R in formula (III)31, R32, R33Independently selected from C1~C4One kind in alkyl, hydrogen, amino；
R in formula (IV)41, R42Independently selected from C1~C4One kind in alkyl, hydrogen, amino；
N is positive integer, meets 2≤n≤100.
2. flame retardant polyurethane according to claim 1, it is characterised in that the phosphorus-nitrogen containing PPG, which is selected from, to be had such as
At least one of 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, it is characterised in that the equal molecule of number of the phosphorus-nitrogen containing PPG
Measure as 350~20000Da.
4. flame retardant polyurethane according to claim 1, it is characterised in that by more containing phosphorus-nitrogen containing PPG, polyethers
The raw material of first alcohol, PEPA and polyisocyanates is prepared in the presence of a catalyst.
5. flame retardant polyurethane according to claim 4, it is characterised in that by weight, catalyst is 0.1~0.3 weight
Part is measured, raw material includes：
The parts by weight of phosphorus-nitrogen containing PPG 10~50；
The parts by weight of PPG 5~50；
The parts by weight of PEPA 2~50；
The parts by weight of polyisocyanates 4~100.
6. flame retardant polyurethane according to claim 4, it is characterised in that by weight, catalyst is 0.1~0.3 weight
Part is measured, raw material includes：
The parts by weight of phosphorus-nitrogen containing PPG 10~50；
The parts by weight of PPG 10~50；
The parts by weight of PEPA 10~50；
The parts by weight of polyisocyanates 5~100.
7. flame retardant polyurethane according to claim 4, it is characterised in that by weight, catalyst is 0.1~0.3 weight
Part is measured, raw material includes：
The parts by weight of phosphorus-nitrogen containing PPG 20；
The parts by weight of PPG 5~25；
The parts by weight of PEPA 2.5~20；
The parts by weight of polyisocyanates 4.2~6.6.
8. according to the flame retardant polyurethane described in any one of claim 4 to 7, it is characterised in that the PPG is selected from poly-
At least one of ethylene glycol dihydric alcohol, polypropylene glycol diols, PolyTHF dihydric alcohol；
The PEPA is selected from polyethylene glycol adipate dihydric alcohol, poly adipate succinic acid ester dihydric alcohol, polycaprolactone
At least one of dihydric alcohol, PCDL；
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 diisocyanates, 1,6- hexa-methylenes two
Cyanate, the dimethylene diisocyanates of 1,12- ten, hexamethylene -1,3- diisocyanate, hexamethylene -1,4- diisocyanate,
IPDI, diphenyl methane 4, oneself is two different by 4- diisocyanate, double-hexyl methane diisocyanate, 1,6-
Cyanate, polymethylene multi-phenenyl isocyanate, XDI, naphthalene -1,5- diisocyanate, methyl cyclohexane
At least one of group diisocyanate, tetramethylxylylene diisocyanate, hydrogenation methylenebis phenyl isocyanate.
9. prepare the method for the flame retardant polyurethane described in any one of claim 4 to 8, it is characterised in that including at least following step
Suddenly：
Phosphorus-nitrogen containing PPG, PPG, PEPA are mixed and by dehydration, add organic solvent, then
Catalyst and polyisocyanates are added, 3~5h is reacted under conditions of 70~100 DEG C, obtains flame retardant polyurethane.
10. according to the method for claim 9, it is characterised in that the mode of the water removal is：100~120 DEG C are warming up to,
Vaccum dewatering 1~3 hour.
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| CN113789113A (en) * | 2021-08-25 | 2021-12-14 | 河北化工医药职业技术学院 | Waterproof coating with flame-retardant and fireproof performances |
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