CN110483735A - A kind of preparation method of Halogen inherent flame retardant aqueous polyurethane film - Google Patents
A kind of preparation method of Halogen inherent flame retardant aqueous polyurethane film Download PDFInfo
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- CN110483735A CN110483735A CN201910817282.7A CN201910817282A CN110483735A CN 110483735 A CN110483735 A CN 110483735A CN 201910817282 A CN201910817282 A CN 201910817282A CN 110483735 A CN110483735 A CN 110483735A
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- halogen
- aqueous polyurethane
- flame retardant
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 80
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 32
- 150000002367 halogens Chemical class 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229920006264 polyurethane film Polymers 0.000 title claims description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 63
- 239000004814 polyurethane Substances 0.000 claims abstract description 40
- 229920002635 polyurethane Polymers 0.000 claims abstract description 40
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000003384 small molecules Chemical class 0.000 claims abstract description 13
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- BZCGWAXQDLXLQM-UHFFFAOYSA-N phosphoryl trichloride Chemical group ClP(Cl)(Cl)=O.ClP(Cl)(Cl)=O BZCGWAXQDLXLQM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920000570 polyether Polymers 0.000 claims abstract description 9
- 235000019260 propionic acid Nutrition 0.000 claims abstract description 9
- 239000005058 Isophorone diisocyanate Substances 0.000 claims abstract description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 8
- 229920005862 polyol Polymers 0.000 claims abstract description 8
- 150000003077 polyols Chemical class 0.000 claims abstract description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 40
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000013019 agitation Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 238000010792 warming Methods 0.000 claims description 11
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 10
- -1 pentaerythrite diphosphate ester Chemical class 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims description 8
- 239000001177 diphosphate Substances 0.000 claims description 8
- 235000011180 diphosphates Nutrition 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- 238000012423 maintenance Methods 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 150000004672 propanoic acids Chemical class 0.000 claims description 5
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims 1
- DJOWTWWHMWQATC-KYHIUUMWSA-N Karpoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1(O)C(C)(C)CC(O)CC1(C)O)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C DJOWTWWHMWQATC-KYHIUUMWSA-N 0.000 claims 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical class CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 8
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 abstract description 4
- 239000004970 Chain extender Substances 0.000 abstract description 3
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 abstract description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 abstract description 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 abstract description 2
- 238000010189 synthetic method Methods 0.000 abstract 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012757 flame retardant agent Substances 0.000 description 2
- 238000002464 physical blending Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
- C07F9/24—Esteramides
- C07F9/2454—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
- C08G18/3889—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus having nitrogen in addition to phosphorus
-
- 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
-
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a kind of preparation methods of Halogen inherent flame retardant aqueous polyurethane, there is by phosphorus oxychloride and pentaerythrite reaction preparation the midbody product of double phosphoryl chloride phosphorus oxychloride functional groups first, then by this midbody product again with the substance reactions such as diglycolamine, prepare a kind of phosphorous, nitrogen ignition-proof element small molecule fire retardant, finally using this small molecule fire retardant as a kind of hard section chain extender and polyether polyol, isophorone diisocyanate, 2, the substance reactions such as 2- dihydromethyl propionic acid prepare a kind of Halogen inherent flame retardant aqueous polyurethane.The present invention is by having prepared the Halogen inherent flame retardant aqueous polyurethane of response type a kind of using a kind of halogen-free flame retardants as a kind of reactive material, good flame retardation effect, synthetic method is simple, cost is relatively low, there is good practicability and economy, has good market prospects.
Description
Technical field
The present invention relates to a kind of preparation methods of Halogen inherent flame retardant aqueous polyurethane film, have thermal stability good, fire-retardant
The high feature of property, belongs to field of functional materials.
Background technique
Aqueous polyurethane (WPU) is the binary colloidal system that water is used as to dispersing agent, possesses many excellent features, such as
Low pollution, nontoxicity, safety height etc., comprehensive performance remains to compared with solvent borne polyurethane.As environment is raw to industry
The raising of production requirement living, aqueous polyurethane can improve the hardness, toughness, moisture resistance, condition of coating due to it significantly
Equal good characteristics show leatherware, timber, clothing in preferable performance, such as industry life in many coating finishing agents.
Compared with the polyurethane of type of solvent, aqueous polyurethane have apparent low-energy-consumption, to the non-stimulated type of the skin of human body, no
Welding is easy the advantages that preparing, is highly-safe.Therefore this but also aqueous polyurethane increasingly attract people sight,
It is increasingly becoming one of the popular application of polyurethane in recent years.
But the property of the high molecular material as specific to itself, aqueous polyurethane have incendive characteristic, the limit
Oxygen index (OI) (LOI) is only 18% or so, so expand the range of its application in order to make up the incendive disadvantage of aqueous polyurethane,
To one of the important development project of the flame-retardant modified and functionalization of waterborne polyurethane of aqueous polyurethane.It is applied for aqueous polyurethane
The flame retarding function method of layer agent can be divided into blending compounding type and inherent flame retardant type.Compounding type is blended to refer to by that will hinder
The material of combustion agent substance and aqueous polyurethane reaches the flame-retardant modified of aqueous polyurethane in a manner of physical blending.Due to addition
Type has the advantages that processing technology is simple, early stage aqueous polyurethane it is flame-retardant modified in have more application.But due to this
Flame-retardant modified mode be in a manner of physical blending, aqueous polyurethane ontology with flame retardant fillers there are degree of scatter, dissolve each other
The disadvantages of property is poor.Addition type would generally use a large amount of flame retardant fillers to carry out flame-proof treatment to aqueous polyurethane, but can generate
Film is uneven, flame retardant fillers usage amount is excessive, easy transfer, water resistant wash the problems such as ability is poor.Inherent flame retardant type is by fire retardant
Flame retardant molecule is introduced into aqueous polyurethane body construction in a manner of chemical bonding and worked as by molecule as a kind of reaction raw materials
In, it is flame-retardant modified to achieve the purpose that.Inherent flame retardant can be inherently overcome on interface and exist from the improvement of molecule angle
Many problems.Flame retardant molecule is added in aqueous polyurethane in a manner of chemical bonding, can significantly reduce fire retardant
Dosage and solves the problems, such as that flame retardant molecule is easily shifted, is lost, in improvement, its is combustible simultaneously, for aqueous polyurethane institute
The features such as distinctive toughness, hardness, condition, influences there is no apparent.According to the class of structural unit in flame-retardant modified polyurethane
Type can be categorized further, as the flame-retardant modified method of soft segment, the flame-retardant modified method of hard section and soft, the fire-retardant modified synergic method of hard section.
Summary of the invention
Technical problems based on background technology, the present invention propose a kind of system of Halogen inherent flame retardant aqueous polyurethane film
Flame retardant molecule is added in aqueous polyurethane by Preparation Method in a manner of chemical bonding, can significantly reduce the agent of fire retardant
It measures and solves the problems, such as that flame retardant molecule is easily shifted, is lost, while having the advantages that flame retardant property is good, thermal stability is high.
In order to solve the above technical problems, the invention adopts the following technical scheme:
A kind of preparation method of Halogen inherent flame retardant aqueous polyurethane film, comprising the following steps:
1, mass fraction is pressed, 17 ~ 34 parts of pentaerythrites are added to the three-necked flask for having reflux unit and exhaust gas processing device, is claimed
115 ~ 230 parts of phosphorus oxychloride are taken, are added in three-necked flask, open magnetic agitation and condensing unit, and start to warm up, system temperature
Degree is warming up to 105 DEG C after reacting 1 ~ 2h when reaching 60 DEG C, and reaction was completed after the reaction was continued 6 ~ 8h, uses methylene chloride and nothing respectively
Water-ethanol is washed, filtered repeatedly and drying, obtains white powder, as two phosphoryl chloride phosphorus oxychloride of midbody product pentaerythrite diphosphate ester
(PDD).
2, mass fraction is pressed, PDD made from 15 ~ 45 parts of steps 1 is added in three-necked flask, sequentially adds 150 ~ 250 parts
Chloroform, 11 ~ 33 parts of diglycolamines, 10 ~ 30 parts of triethylamines are in three-necked flask, and ice-water bath maintenance system reaction temperature is 10 ~ 15
Between DEG C, react 2 ~ 3h, after be warming up to 30 DEG C, the reaction was continued 4 ~ 5h steams chloroform and with acetone and anhydrous second after reaction was completed
Alcohol mixed solvent washs product, is purified, and white powdery solids product is prepared, as a kind of to contain the fire-retardant member of phosphorus nitrogen
The small molecule fire retardant (PDL) of element.
3, mass fraction is pressed, by 15 ~ 45 parts of polyether polyol after drying, 14.5 ~ 43.5 parts of isophorone diisocyanates
Three-necked flask is added in ester, 1.8 ~ 5.4 parts of 2,2- dihydromethyl propionic acids and 1.5 ~ 4.5 parts of catalyst dibutyltin dilaurylates, adds
Entering 100 ~ 150 parts of acetone, opens magnetic agitation and condenser system, control system temperature reacts 3h to 80 DEG C, then it is added 2.2 ~
6.6 parts of 1,4-butanediol, 1.44 ~ 9.7 parts of PDL and 5 ~ 10 part of acetone are in three-necked flask, the reaction was continued 3 ~ 5h, then addition
1.2 ~ 3.6 parts of triethylamines, while 60 DEG C are cooled to, the reaction was continued at 60 DEG C 30min, 60 ~ 208 parts of distilled water of addition, continuation
30min is reacted, reaction was completed.
4, step 3 is reacted solution obtained to pour into polyfluortetraethylene plate, is stood for 24 hours, so the dry 36h system at 60 DEG C
Obtain Halogen inherent flame retardant aqueous polyurethane film.
The highest content of fire retardant is 8.7% in this Halogen inherent flame retardant aqueous polyurethane.
The Halogen inherent flame retardant aqueous polyurethane film prepared according to the method described above.
Beneficial effects of the present invention: the present invention proposes a kind of Halogen inherent flame retardant aqueous polyurethane film, using phosphorus oxychloride
It is reacted with pentaerythrite, the product of preparation reacts in acetonitrile solvent with diglycolamine, triethylamine again prepares a kind of phosphorous, nitrogen
The solid small molecule Halogen inherent flame retardant agent of element, it is finally more using the fire retardant of preparation as a kind of small molecule chain extender and polyethers
A kind of Halogen essence resistance is made in first alcohol, isophorone diisocyanate, butanediol and 2, the substance reactions such as 2- dihydromethyl propionic acid
Aqueous polyurethane is fired, flame retardant molecule is added in aqueous polyurethane in a manner of chemical bonding, can significantly be reduced fire-retardant
The dosage of agent and solves the problems, such as that flame retardant molecule easily shifts, the aqueous polyurethane that is lost, while preparing is with flame retardant property
Well, the advantages that thermal stability is high.
Detailed description of the invention
Fig. 1 is the thermal multigraph of fire retardant PDL made from embodiment 1.
Specific embodiment
Combined with specific embodiments below, the present invention will be further described.It should be understood that following embodiment is merely to illustrate this
The person skilled in the art of the range of invention and is not intended to limit the present invention, the field can make one according to the content of foregoing invention
A little nonessential modifications and adaptations.
Embodiment 1
The preparation method of the Halogen inherent flame retardant aqueous polyurethane film of the present embodiment, steps are as follows:
1, mass fraction is pressed, 17 parts of pentaerythrites are added to the three-necked flask for having reflux unit and exhaust gas processing device, are weighed
115 parts of phosphorus oxychloride, are added in three-necked flask, open magnetic agitation and condensing unit, and start to warm up, system temperature reaches
At 60 DEG C, 105 DEG C are warming up to after reacting 1h, reaction was completed after the reaction was continued 6h, respectively repeatedly with methylene chloride and dehydrated alcohol
Washing, suction filtration and drying, obtain white powder, as two phosphoryl chloride phosphorus oxychloride of midbody product pentaerythrite diphosphate ester (PDD).
2, mass fraction is pressed, PDD made from 15 parts of steps 1 is added in three-necked flask, sequentially adds 150 parts of chloroforms, 11
Part diglycolamine, for 10 parts of triethylamines in three-necked flask, ice-water bath maintenance system reaction temperature reacts 2h between 10 ~ 15 DEG C,
After be warming up to 30 DEG C, the reaction was continued 4h, steamed after reaction was completed chloroform and with acetone and dehydrated alcohol mixed solvent to product into
Row washing, purification, prepare white powdery solids product, as a kind of small molecule fire retardant containing phosphorus nitrogen ignition-proof element
(PDL).
3, mass fraction is pressed, by 15 parts of polyether polyol, the 14.5 parts of isophorone diisocyanate, 1.8 parts after drying
Three-necked flask is added in 2,2- dihydromethyl propionic acids and 1.5 parts of catalyst dibutyltin dilaurylates, and 100 parts of acetone are added, open
Magnetic agitation and condenser system, control system temperature react 3h to 80 DEG C, then 1.95 parts of 1,4-butanediol of addition, and 1.44 parts
PDL and 5 part of acetone is in three-necked flask, the reaction was continued 3h, 1.2 parts of triethylamines is then added, while being cooled to 60 DEG C, at 60 DEG C
Lower the reaction was continued 30min, is added 67 parts of distilled water, the reaction was continued 30min, and reaction was completed.
4, step 3 is reacted solution obtained to pour into polyfluortetraethylene plate, is stood for 24 hours, so the dry 36h system at 60 DEG C
Obtain Halogen inherent flame retardant aqueous polyurethane film.
Embodiment 2
The preparation method of the Halogen inherent flame retardant aqueous polyurethane film of the present embodiment, steps are as follows:
1, mass fraction is pressed, 25.5 parts of pentaerythrites are added to the three-necked flask for having reflux unit and exhaust gas processing device, is claimed
170 parts of phosphorus oxychloride are taken, are added in three-necked flask, open magnetic agitation and condensing unit, and start to warm up, system temperature reaches
When to 60 DEG C, 105 DEG C are warming up to after reacting 1.5h, reaction was completed after the reaction was continued 7h, uses methylene chloride and dehydrated alcohol respectively
It washs, filter repeatedly and is dry, obtain white powder, as two phosphoryl chloride phosphorus oxychloride of midbody product pentaerythrite diphosphate ester (PDD).
2, mass fraction is pressed, PDD made from 30 parts of steps 1 is added in three-necked flask, sequentially adds 200 parts of chloroforms, 22
Part diglycolamine, 20 parts of triethylamines are in three-necked flask, and ice-water bath maintenance system reaction temperature is between 10 ~ 15 DEG C, reaction
2.5h, after be warming up to 30 DEG C, the reaction was continued 4.5h steams chloroform and with acetone and dehydrated alcohol mixed solvent pair after reaction was completed
Product is washed, is purified, and white powdery solids product, as a kind of small molecule resistance containing phosphorus nitrogen ignition-proof element are prepared
It fires agent (PDL).
3, mass fraction is pressed, by 30 parts of polyether polyol, the 29 parts of isophorone diisocyanate, 3.6 part 2 after drying,
Three-necked flask is added in 2- dihydromethyl propionic acid and 3 parts of catalyst dibutyltin dilaurylates, and 125 parts of acetone are added, open magnetic force
Stirring and condenser system, control system temperature react 3h to 80 DEG C, 3.7 parts of 1,4-butanediol, 4.5 parts of PDL and 8 are then added
Part acetone is in three-necked flask, and the reaction was continued 4h is then added 2.4 parts of triethylamines, while being cooled to 60 DEG C, continues at 60 DEG C
30min is reacted, 136 parts of distilled water are added, the reaction was continued 30min, reaction was completed.
4, step 3 is reacted solution obtained to pour into polyfluortetraethylene plate, is stood for 24 hours, so the dry 36h system at 60 DEG C
Obtain Halogen inherent flame retardant aqueous polyurethane film.
Embodiment 3
The preparation method of the Halogen inherent flame retardant aqueous polyurethane film of the present embodiment, steps are as follows:
1, mass fraction is pressed, 34 parts of pentaerythrites are added to the three-necked flask for having reflux unit and exhaust gas processing device, are weighed
230 parts of phosphorus oxychloride, are added in three-necked flask, open magnetic agitation and condensing unit, and start to warm up, system temperature reaches
At 60 DEG C, 105 DEG C are warming up to after reacting 2h, reaction was completed after the reaction was continued 8h, respectively repeatedly with methylene chloride and dehydrated alcohol
Washing, suction filtration and drying, obtain white powder, as two phosphoryl chloride phosphorus oxychloride of midbody product pentaerythrite diphosphate ester (PDD).
2, mass fraction is pressed, PDD made from 45 parts of steps 1 is added in three-necked flask, sequentially adds 250 parts of chloroforms, 33
Part diglycolamine, for 30 parts of triethylamines in three-necked flask, ice-water bath maintenance system reaction temperature reacts 3h between 10 ~ 15 DEG C,
After be warming up to 30 DEG C, the reaction was continued 5h, steamed after reaction was completed chloroform and with acetone and dehydrated alcohol mixed solvent to product into
Row washing, purification, prepare white powdery solids product, as a kind of small molecule fire retardant containing phosphorus nitrogen ignition-proof element
(PDL).
3, mass fraction is pressed, by 45 parts of polyether polyol, the 43.5 parts of isophorone diisocyanate, 5.4 parts after drying
Three-necked flask is added in 2,2- dihydromethyl propionic acids and 4.5 parts of catalyst dibutyltin dilaurylates, and 150 parts of acetone are added, open
Magnetic agitation and condenser system, control system temperature react 3h to 80 DEG C, 5.2 parts of 1,4-butanediol, 7.9 parts of PDL are then added
With 10 parts of acetone in three-necked flask, the reaction was continued 5h is then added 3.6 parts of triethylamines, while being cooled to 60 DEG C, at 60 DEG C
The reaction was continued 30min, is added 195 parts of distilled water, the reaction was continued 30min, and reaction was completed.
4, step 3 is reacted solution obtained to pour into polyfluortetraethylene plate, is stood for 24 hours, so the dry 36h system at 60 DEG C
Obtain Halogen inherent flame retardant aqueous polyurethane film.
Embodiment 4
The preparation method of the Halogen inherent flame retardant aqueous polyurethane film of the present embodiment, steps are as follows:
1, mass fraction is pressed, 34 parts of pentaerythrites are added to the three-necked flask for having reflux unit and exhaust gas processing device, are weighed
230 parts of phosphorus oxychloride, are added in three-necked flask, open magnetic agitation and condensing unit, and start to warm up, system temperature reaches
At 60 DEG C, 105 DEG C are warming up to after reacting 2h, reaction was completed after the reaction was continued 8h, respectively repeatedly with methylene chloride and dehydrated alcohol
Washing, suction filtration and drying, obtain white powder, as two phosphoryl chloride phosphorus oxychloride of midbody product pentaerythrite diphosphate ester (PDD).
2, mass fraction is pressed, PDD made from 45 parts of steps 1 is added in three-necked flask, sequentially adds 250 parts of chloroforms, 33
Part diglycolamine, for 30 parts of triethylamines in three-necked flask, ice-water bath maintenance system reaction temperature reacts 3h between 10 ~ 15 DEG C,
After be warming up to 30 DEG C, the reaction was continued 5h, steamed after reaction was completed chloroform and with acetone and dehydrated alcohol mixed solvent to product into
Row washing, purification, prepare white powdery solids product, as a kind of small molecule fire retardant containing phosphorus nitrogen ignition-proof element
(PDL).
3, mass fraction is pressed, by 45 parts of polyether polyol, the 43.5 parts of isophorone diisocyanate, 5.4 parts after drying
Three-necked flask is added in 2,2- dihydromethyl propionic acids and 4.5 parts of catalyst dibutyltin dilaurylates, and 150 parts of acetone are added, open
Magnetic agitation and condenser system, control system temperature react 3h to 80 DEG C, 4.8 parts of 1,4-butanediol, 9.7 parts of PDL are then added
With 10 parts of acetone in three-necked flask, the reaction was continued 5h is then added 3.6 parts of triethylamines, while being cooled to 60 DEG C, at 60 DEG C
The reaction was continued 30min, is added 208 parts of distilled water, the reaction was continued 30min, and reaction was completed.
4, step 3 is reacted solution obtained to pour into polyfluortetraethylene plate, is stood for 24 hours, so the dry 36h system at 60 DEG C
Obtain Halogen inherent flame retardant aqueous polyurethane film.
It will be seen from figure 1 that carbon left is up to 50 or more percent after fire retardant burning at 550 DEG C, it is higher residual
More residue can be generated after showing extinguishing waterborn polyurethane material burning in charcoal amount, and covering material surface can effectively play
The effect of Combustion Source is isolated, reaches good flame retardant effect.
Comparative example
The preparation method of the Halogen aqueous polyurethane of this comparative example, steps are as follows:
1, mass fraction is pressed, by 15 parts of polyether polyol, the 14.5 parts of isophorone diisocyanate, 1.8 part 2,2- after drying
Three-necked flask is added in dihydromethyl propionic acid and 1.5 parts of catalyst dibutyltin dilaurylates, and 100 parts of acetone are added, open magnetic force
Stirring and condenser system, control system temperature react 3h to 80 DEG C.Then 2.2 parts of 1,4- butanediols and 5 parts of acetone are added in three
In mouthful flask, 1.2 parts of triethylamines are then added, while being cooled to 60 DEG C in the reaction was continued 3h, the reaction was continued at 60 DEG C 30min,
60 parts of distilled water are added, the reaction was continued 30min, reaction was completed.
2, step 1 is reacted solution obtained to pour into polyfluortetraethylene plate, is stood for 24 hours, so the dry 36h system at 60 DEG C
Obtain Halogen aqueous polyurethane film.
1 extinguishing waterborn polyurethane flammability of table
| Sample | Flame retardant agent content (%) | Flammability |
| Comparative example | 0 | It is flammable |
| Embodiment 1 | 4.2 | It is non-combustible |
| Embodiment 2 | 6.1 | It is non-combustible |
| Embodiment 3 | 7.1 | It is non-combustible |
| Embodiment 4 | 8.7 | It is non-combustible |
As it can be seen from table 1 the addition of fire retardant has certain anti-flammability to aqueous polyurethane, additive amount be 4.2% when
It waits, water-base polyurethane material is non-combustible in air, illustrates that the extinguishing waterborn polyurethane prepared exists in less fire retardant
Under conditions of have good flame retardancy.
The present invention synthesizes a kind of phosphorous, nitrogen ignition-proof element solid small molecule halogen-free flame retardants, then this is had reaction
The fire retardant of property is introduced into aqueous polyurethane system as a kind of chain extender, and it is aqueous poly- to prepare a kind of Halogen inherent flame retardant
Urethane, the substance for playing fire retardation are inserted into rigid polyurethane segment structure by the existence form of small molecule, have flame retardant effect
Phosphorus, nitrogen greatly improve the temperature of initial decomposition of polyurethane material, effectively improve the flame retardant effect of polyurethane material.
Basic principles and main features and advantages of the present invention of the invention have been shown and described above.The skill of the industry
Art personnel it should be appreciated that the present invention is not limited to the above embodiments, the above embodiments and description only describe
The principle of the present invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these
Changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and
Its equivalent thereof.
Claims (5)
1. a kind of preparation method of Halogen inherent flame retardant aqueous polyurethane film, it is characterised in that poly- including following step:
The preparation of S1, two phosphoryl chloride phosphorus oxychloride PDD of midbody product pentaerythrite diphosphate ester；
The preparation of S2, small molecule fire retardant PDL containing phosphorus nitrogen ignition-proof element；
S3, press mass fraction, by after drying 15 ~ 45 parts of polyether polyol, 14.5 ~ 43.5 parts of isophorone diisocyanate,
Three-necked flask is added in 1.8 ~ 5.4 parts of 2,2- dihydromethyl propionic acids and 1.5 ~ 4.5 parts of dibutyl tin dilaurates, is added 100 ~ 150
Part acetone, opens magnetic agitation and condenser system, and control system temperature reacts 3h to 80 DEG C, and 2.2 ~ 6.6 parts of Isosorbide-5-Nitraes-are then added
Butanediol, 1.44 ~ 9.7 parts of PDL and 5 ~ 10 part of acetone are in three-necked flask, the reaction was continued 3 ~ 5h, then 1.2 ~ 3.6 part three of addition
60 ~ 208 parts of distilled water are added in ethamine, while being cooled to 60 DEG C, the reaction was continued at 60 DEG C 30min, the reaction was continued 30min, knot
Shu Fanying；
S4, S3 reaction solution obtained is poured into polyfluortetraethylene plate, is stood for 24 hours, then nothing is made in dry 36h at 60 DEG C
Halogen inherent flame retardant aqueous polyurethane film.
2. the preparation method of Halogen inherent flame retardant aqueous polyurethane film according to claim 1, it is characterised in that: the step
Suddenly two phosphoryl chloride phosphorus oxychloride of (1) midbody product pentaerythrite diphosphate ester the preparation method is as follows: press mass fraction, by 17 ~ 34 parts of seasons
The three-necked flask for having reflux unit and exhaust gas processing device is added in penta tetrol, weighs 115 ~ 230 parts of phosphorus oxychloride and is added to three
In mouth flask, magnetic agitation and condensing unit are opened, and start to warm up, when system temperature reaches 60 DEG C, heated up after reacting 1 ~ 2h
To 105 DEG C, reaction was completed after the reaction was continued 6 ~ 8h, wash, is filtered repeatedly and dried with methylene chloride and dehydrated alcohol respectively, obtained
To white powder, as two phosphoryl chloride phosphorus oxychloride of midbody product pentaerythrite diphosphate ester (PDD).
3. the preparation method of Halogen inherent flame retardant aqueous polyurethane film according to claim 1, it is characterised in that: the step
Suddenly the preparation method of the small molecule fire retardant PDL of (2) containing phosphorus nitrogen ignition-proof element is as follows；By mass fraction, by 15 ~ 45 parts of S1 systems
The PDD obtained is added in three-necked flask, sequentially adds 150 ~ 250 parts of chloroforms, 11 ~ 33 parts of diglycolamines, 10 ~ 30 parts of triethylamines are in three
In mouthful flask, ice-water bath maintenance system reaction temperature reacts 2 ~ 3h between 10 ~ 15 DEG C, after be warming up to 30 DEG C, the reaction was continued 4 ~
5h steams chloroform and is washed, purified to product with acetone and dehydrated alcohol mixed solvent, prepares white after reaction was completed
Pulverulent solids product, as the small molecule fire retardant PDL containing phosphorus nitrogen ignition-proof element.
4. the preparation method of Halogen inherent flame retardant aqueous polyurethane film according to claim 1, it is characterised in that: the nothing
The highest content of fire retardant PDL is 8.7% in halogen inherent flame retardant aqueous polyurethane film.
5. utilizing Halogen inherent flame retardant aqueous polyurethane made from any method of claim 1-5.
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