CN110483735B - Preparation method of halogen-free intrinsic flame-retardant waterborne polyurethane film - Google Patents
Preparation method of halogen-free intrinsic flame-retardant waterborne polyurethane film Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 91
- 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 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229920006264 polyurethane film Polymers 0.000 title claims description 23
- 239000004814 polyurethane Substances 0.000 claims abstract description 44
- 229920002635 polyurethane Polymers 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000013067 intermediate product Substances 0.000 claims abstract description 10
- 239000005058 Isophorone diisocyanate Substances 0.000 claims abstract description 9
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 9
- 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
- 229920000570 polyether Polymers 0.000 claims abstract description 9
- 229920005862 polyol Polymers 0.000 claims abstract description 9
- 150000003077 polyols Chemical class 0.000 claims abstract description 9
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims abstract description 8
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 claims abstract description 8
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 42
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 40
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 238000003760 magnetic stirring Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- -1 polytetrafluoroethylene Polymers 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 8
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims description 7
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 239000012265 solid product Substances 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- IITOXVPDCDQIOP-UHFFFAOYSA-N P(=O)(OP(=O)(Cl)Cl)(Cl)Cl.P(=O)(O)OP(=O)O.OCC(CO)(CO)CO Chemical compound P(=O)(OP(=O)(Cl)Cl)(Cl)Cl.P(=O)(O)OP(=O)O.OCC(CO)(CO)CO IITOXVPDCDQIOP-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- RLXOKISGPALBEB-UHFFFAOYSA-N OP(=O)OP(O)=O.OCC(CO)(CO)CO Chemical compound OP(=O)OP(O)=O.OCC(CO)(CO)CO RLXOKISGPALBEB-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
- 230000000694 effects Effects 0.000 abstract description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 4
- 239000011574 phosphorus Substances 0.000 abstract description 4
- 239000004970 Chain extender Substances 0.000 abstract description 3
- 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
- KUWPCJHYPSUOFW-UHFFFAOYSA-N 2-(hydroxymethyl)-6-(2-nitrophenoxy)oxane-3,4,5-triol Chemical group OC1C(O)C(O)C(CO)OC1OC1=CC=CC=C1[N+]([O-])=O KUWPCJHYPSUOFW-UHFFFAOYSA-N 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000002715 modification method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
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- 238000007306 functionalization reaction Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- DKLLESQJDRRRJO-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;phosphono dihydrogen phosphate Chemical compound OCC(CO)(CO)CO.OP(O)(=O)OP(O)(O)=O DKLLESQJDRRRJO-UHFFFAOYSA-N 0.000 description 1
- 241001131796 Botaurus stellaris Species 0.000 description 1
- 230000006978 adaptation 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
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 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
- 238000002464 physical blending Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic 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
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
- C08G18/3889—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus having nitrogen in addition to phosphorus
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- 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
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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
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
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- 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
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- 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
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Abstract
The invention discloses a preparation method of halogen-free intrinsic flame retardant waterborne polyurethane, which comprises the steps of firstly preparing an intermediate product with a diphosphoryl chloride functional group by reacting phosphorus oxychloride and pentaerythritol, then reacting the intermediate product with substances such as diglycolamine and the like to prepare a micromolecule flame retardant containing phosphorus and nitrogen flame retardant elements, and finally reacting the micromolecule flame retardant serving as a hard segment chain extender with substances such as polyether polyol, isophorone diisocyanate and 2, 2-dimethylolpropionic acid to prepare the halogen-free intrinsic flame retardant waterborne polyurethane. The reactive halogen-free intrinsic flame-retardant waterborne polyurethane is prepared by taking a halogen-free flame retardant as a reaction substance, and has the advantages of good flame-retardant effect, simple synthesis method, lower cost, good practicability and economy and good market prospect.
Description
Technical Field
The invention relates to a preparation method of a halogen-free intrinsic flame-retardant waterborne polyurethane film, which has the characteristics of good thermal stability and high flame retardance and belongs to the field of functional materials.
Background
Waterborne Polyurethane (WPU) is a binary colloid system using water as a dispersing agent, has many excellent characteristics such as low pollution, no toxicity, high safety and the like, and the comprehensive performance of the waterborne polyurethane can still be compared with that of solvent-based polyurethane. With the increasing requirements of the environment on industrial life and production, the waterborne polyurethane can remarkably improve the excellent characteristics of hardness, toughness, moisture resistance, appearance and the like of the coating, and shows better performance in various coating finishing agents, such as leatherware, wood, clothes and the like in industrial life. Compared with solvent type polyurethane, the waterborne polyurethane has the advantages of obvious low energy consumption, no stimulation to human skin, no environmental damage, easy preparation, high safety and the like. This also makes waterborne polyurethanes increasingly attractive to people and is becoming one of the popular applications of polyurethanes in recent years.
However, because of the properties of the polymer materials unique to the waterborne polyurethane, the waterborne polyurethane has the characteristic of easy combustion, and the Limit Oxygen Index (LOI) is only about 18%, so in order to overcome the defect of easy combustion of the waterborne polyurethane and expand the application range of the waterborne polyurethane, the flame retardant modification of the waterborne polyurethane is also one of the important development problems of the functionalization of the waterborne polyurethane. Flame-retardant functionalization methods for aqueous polyurethane coating agents can be divided into blending and compounding types and intrinsic flame-retardant types. The blending and compounding type is that the flame retardant substance and the material of the waterborne polyurethane are physically blended to achieve the flame retardant modification of the waterborne polyurethane. The additive type polyurethane has the advantage of simple processing technology, and has more application in the early flame retardant modification of waterborne polyurethane. However, the flame retardant modification mode is a physical blending mode, so that the water-based polyurethane body and the flame retardant filler have the defects of poor dispersion degree, poor intersolubility and the like. The additive type polyurethane is usually subjected to flame retardant finishing by using a large amount of flame retardant filler, but the problems of uneven coating, excessive use amount of the flame retardant filler, easy transfer, poor washing resistance and the like are caused. The intrinsic flame retardance is that flame retardant molecules are used as a reaction raw material and introduced into the body structure of the waterborne polyurethane in a chemical bonding mode so as to achieve the purpose of flame retardance modification. Intrinsic flame retardancy is an improvement from a molecular point of view that can essentially overcome many of the problems present at the interface. The flame retardant molecules are added into the waterborne polyurethane in a chemical bonding mode, so that the dosage of the flame retardant can be obviously reduced, the problem that the flame retardant molecules are easy to transfer and run off is solved, the combustibility of the waterborne polyurethane is improved, and meanwhile, the special characteristics of toughness, hardness, appearance and the like of the waterborne polyurethane are not obviously influenced. According to the type of structural units in the flame-retardant modified polyurethane, the flame-retardant modified polyurethane can be further classified into a soft-segment flame-retardant modification method, a hard-segment flame-retardant modification method and a soft-and hard-segment flame-retardant synergistic modification method.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a preparation method of a halogen-free flame-retardant waterborne polyurethane film, which is characterized in that flame retardant molecules are added into waterborne polyurethane in a chemical bonding mode, so that the dosage of a flame retardant can be obviously reduced, the problems that the flame retardant molecules are easy to transfer and run off are solved, and the halogen-free flame-retardant waterborne polyurethane film has the advantages of good flame retardant property and high thermal stability.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of a halogen-free intrinsic flame-retardant waterborne polyurethane film comprises the following steps:
1. adding 17-34 parts of pentaerythritol into a three-neck flask with a reflux device and a tail gas treatment device according to parts by weight, weighing 115-230 parts of phosphorus oxychloride, adding the phosphorus oxychloride into the three-neck flask, starting a magnetic stirring and condensing device, starting heating, reacting for 1-2 hours when the system temperature reaches 60 ℃, heating to 105 ℃, continuing to react for 6-8 hours, finishing the reaction, repeatedly washing with dichloromethane and absolute ethyl alcohol, carrying out suction filtration and drying respectively, and obtaining white powder, namely an intermediate product pentaerythritol diphosphonate diphosphoryl chloride (PDD).
2. Adding 15-45 parts by weight of the PDD prepared in the step 1 into a three-neck flask, sequentially adding 150-250 parts by weight of chloroform, 11-33 parts by weight of diglycolamine and 10-30 parts by weight of triethylamine into the three-neck flask, maintaining the reaction temperature of the system at 10-15 ℃ in an ice-water bath, reacting for 2-3 h, heating to 30 ℃, continuing to react for 4-5 h, evaporating chloroform after the reaction is finished, washing and purifying the product by using a mixed solvent of acetone and absolute ethyl alcohol, and preparing a white powder solid product, namely the micromolecular flame retardant (PDL) containing the phosphorus-nitrogen flame retardant element.
3. Adding 15-45 parts of dried polyether polyol, 14.5-43.5 parts of isophorone diisocyanate, 1.8-5.4 parts of 2, 2-dimethylolpropionic acid and 1.5-4.5 parts of catalyst dibutyltin dilaurate into a three-neck flask, adding 100-150 parts of acetone, starting a magnetic stirring and condensing system, controlling the temperature of the system to 80 ℃, reacting for 3 hours, then adding 2.2-6.6 parts of 1, 4-butanediol, 1.44-9.7 parts of PDL and 5-10 parts of acetone into the three-neck flask, continuing to react for 3-5 hours, then adding 1.2-3.6 parts of triethylamine, simultaneously cooling to 60 ℃, continuing to react for 30 minutes at 60 ℃, adding 60-208 parts of distilled water, continuing to react for 30 minutes, and finishing the reaction.
4. And (3) pouring the solution prepared by the reaction in the step (3) into a polytetrafluoroethylene plate, standing for 24h, and then drying for 36h at the temperature of 60 ℃ to prepare the halogen-free intrinsic flame-retardant waterborne polyurethane film.
The highest content of the flame retardant in the halogen-free intrinsic flame-retardant waterborne polyurethane is 8.7 percent.
The halogen-free intrinsic flame-retardant waterborne polyurethane film prepared by the method.
The invention has the beneficial effects that: the invention provides a halogen-free intrinsic flame-retardant waterborne polyurethane film, which is prepared by reacting phosphorus oxychloride with pentaerythritol, reacting the prepared product with diglycolamine and triethylamine in an acetonitrile solvent to prepare a solid micromolecule halogen-free intrinsic flame retardant containing phosphorus and nitrogen elements, and finally reacting the prepared flame retardant serving as a micromolecule chain extender with polyether polyol, isophorone diisocyanate, butanediol, 2-dimethylolpropionic acid and other substances to prepare halogen-free intrinsic flame-retardant waterborne polyurethane.
Drawings
FIG. 1 is a thermogravimetric diagram of a flame retardant PDL obtained in example 1.
Detailed Description
The present invention will be further described with reference to the following examples. It is to be understood that the following examples are illustrative only and are not intended to limit the scope of the invention, which is to be given numerous insubstantial modifications and adaptations by those skilled in the art based on the teachings set forth above.
Example 1
The preparation method of the halogen-free intrinsic flame-retardant waterborne polyurethane film comprises the following steps:
1. adding 17 parts by mass of pentaerythritol into a three-neck flask with a reflux device and a tail gas treatment device, weighing 115 parts by mass of phosphorus oxychloride, adding the phosphorus oxychloride into the three-neck flask, starting a magnetic stirring and condensing device, starting heating, reacting for 1 hour until the system temperature reaches 60 ℃, heating to 105 ℃, continuing to react for 6 hours, finishing the reaction, repeatedly washing with dichloromethane and absolute ethyl alcohol, carrying out suction filtration and drying respectively, and obtaining white powder, namely an intermediate product pentaerythritol diphosphoric acid dichloride (PDD).
2. Adding 15 parts by mass of PDD prepared in the step 1 into a three-neck flask, sequentially adding 150 parts of chloroform, 11 parts of diglycolamine and 10 parts of triethylamine into the three-neck flask, maintaining the reaction temperature of the system between 10 and 15 ℃ in an ice-water bath, reacting for 2 hours, heating to 30 ℃, continuing to react for 4 hours, evaporating chloroform after the reaction is finished, washing and purifying the product by using a mixed solvent of acetone and absolute ethyl alcohol, and preparing a white powdery solid product, namely the micromolecular flame retardant (PDL) containing phosphorus-nitrogen flame retardant elements.
3. Adding 15 parts of dried polyether polyol, 14.5 parts of isophorone diisocyanate, 1.8 parts of 2, 2-dimethylolpropionic acid and 1.5 parts of catalyst dibutyltin dilaurate into a three-neck flask, adding 100 parts of acetone, starting a magnetic stirring and condensing system, controlling the temperature of the system to 80 ℃, reacting for 3 hours, adding 1.95 parts of 1, 4-butanediol, 1.44 parts of PDL and 5 parts of acetone into the three-neck flask, continuously reacting for 3 hours, then adding 1.2 parts of triethylamine, simultaneously cooling to 60 ℃, continuously reacting for 30 minutes at 60 ℃, adding 67 parts of distilled water, continuously reacting for 30 minutes, and finishing the reaction.
4. And (3) pouring the solution prepared by the reaction in the step (3) into a polytetrafluoroethylene plate, standing for 24h, and then drying for 36h at the temperature of 60 ℃ to prepare the halogen-free intrinsic flame-retardant waterborne polyurethane film.
Example 2
The preparation method of the halogen-free intrinsic flame-retardant waterborne polyurethane film comprises the following steps:
1. adding 25.5 parts of pentaerythritol into a three-neck flask with a reflux device and a tail gas treatment device according to the parts by weight, weighing 170 parts of phosphorus oxychloride, adding the phosphorus oxychloride into the three-neck flask, starting a magnetic stirring and condensing device, starting heating, reacting for 1.5 hours when the system temperature reaches 60 ℃, heating to 105 ℃, continuing to react for 7 hours, finishing the reaction, repeatedly washing with dichloromethane and absolute ethyl alcohol, carrying out suction filtration and drying respectively, and obtaining white powder, namely an intermediate product pentaerythritol diphosphonate diphosphoryl chloride (PDD).
2. Adding 30 parts by weight of PDD prepared in the step 1 into a three-neck flask, sequentially adding 200 parts of chloroform, 22 parts of diglycolamine and 20 parts of triethylamine into the three-neck flask, maintaining the reaction temperature of the system between 10 and 15 ℃ in an ice-water bath, reacting for 2.5 hours, heating to 30 ℃, continuing to react for 4.5 hours, evaporating chloroform after the reaction is finished, washing and purifying the product by using a mixed solvent of acetone and absolute ethyl alcohol, and preparing a white powdery solid product, namely the micromolecular flame retardant (PDL) containing phosphorus-nitrogen flame retardant elements.
3. Adding 30 parts of dried polyether polyol, 29 parts of isophorone diisocyanate, 3.6 parts of 2, 2-dimethylolpropionic acid and 3 parts of catalyst dibutyltin dilaurate into a three-neck flask, adding 125 parts of acetone, starting a magnetic stirring and condensing system, controlling the temperature of the system to 80 ℃, reacting for 3 hours, adding 3.7 parts of 1, 4-butanediol, 4.5 parts of PDL and 8 parts of acetone into the three-neck flask, continuously reacting for 4 hours, then adding 2.4 parts of triethylamine, simultaneously cooling to 60 ℃, continuously reacting for 30 minutes at 60 ℃, adding 136 parts of distilled water, continuously reacting for 30 minutes, and finishing the reaction.
4. And (3) pouring the solution prepared by the reaction in the step (3) into a polytetrafluoroethylene plate, standing for 24h, and then drying for 36h at the temperature of 60 ℃ to prepare the halogen-free intrinsic flame-retardant waterborne polyurethane film.
Example 3
The preparation method of the halogen-free intrinsic flame-retardant waterborne polyurethane film comprises the following steps:
1. adding 34 parts by mass of pentaerythritol into a three-neck flask with a reflux device and a tail gas treatment device, weighing 230 parts by mass of phosphorus oxychloride, adding the phosphorus oxychloride into the three-neck flask, starting a magnetic stirring and condensing device, starting heating, reacting for 2 hours when the system temperature reaches 60 ℃, heating to 105 ℃, continuing to react for 8 hours, finishing the reaction, repeatedly washing with dichloromethane and absolute ethyl alcohol, carrying out suction filtration and drying respectively, and obtaining white powder, namely an intermediate product pentaerythritol diphosphonate diphosphoryl chloride (PDD).
2. Adding 45 parts by weight of PDD prepared in the step 1 into a three-neck flask, sequentially adding 250 parts of chloroform, 33 parts of diglycolamine and 30 parts of triethylamine into the three-neck flask, maintaining the reaction temperature of the system between 10 and 15 ℃ in an ice-water bath, reacting for 3 hours, heating to 30 ℃, continuing to react for 5 hours, evaporating chloroform after the reaction is finished, washing and purifying the product by using a mixed solvent of acetone and absolute ethyl alcohol, and preparing a powdery solid product, namely a micromolecular flame retardant (PDL) containing phosphorus-nitrogen flame retardant elements.
3. Adding 45 parts of dried polyether polyol, 43.5 parts of isophorone diisocyanate, 5.4 parts of 2, 2-dimethylolpropionic acid and 4.5 parts of catalyst dibutyltin dilaurate into a three-neck flask, adding 150 parts of acetone, starting a magnetic stirring and condensing system, controlling the temperature of the system to 80 ℃, reacting for 3 hours, adding 5.2 parts of 1, 4-butanediol, 7.9 parts of PDL and 10 parts of acetone into the three-neck flask, continuing to react for 5 hours, then adding 3.6 parts of triethylamine, simultaneously cooling to 60 ℃, continuing to react for 30 minutes at 60 ℃, adding 195 parts of distilled water, continuing to react for 30 minutes, and finishing the reaction.
4. And (3) pouring the solution prepared by the reaction in the step (3) into a polytetrafluoroethylene plate, standing for 24h, and then drying for 36h at the temperature of 60 ℃ to prepare the halogen-free intrinsic flame-retardant waterborne polyurethane film.
Example 4
The preparation method of the halogen-free intrinsic flame-retardant waterborne polyurethane film comprises the following steps:
1. adding 34 parts by mass of pentaerythritol into a three-neck flask with a reflux device and a tail gas treatment device, weighing 230 parts by mass of phosphorus oxychloride, adding the phosphorus oxychloride into the three-neck flask, starting a magnetic stirring and condensing device, starting heating, reacting for 2 hours when the system temperature reaches 60 ℃, heating to 105 ℃, continuing to react for 8 hours, finishing the reaction, repeatedly washing with dichloromethane and absolute ethyl alcohol, carrying out suction filtration and drying respectively, and obtaining white powder, namely an intermediate product pentaerythritol diphosphonate diphosphoryl chloride (PDD).
2. Adding 45 parts by weight of PDD prepared in the step 1 into a three-neck flask, sequentially adding 250 parts of chloroform, 33 parts of diglycolamine and 30 parts of triethylamine into the three-neck flask, maintaining the reaction temperature of the system between 10 and 15 ℃ in an ice-water bath, reacting for 3 hours, heating to 30 ℃, continuing to react for 5 hours, evaporating chloroform after the reaction is finished, washing and purifying the product by using a mixed solvent of acetone and absolute ethyl alcohol, and preparing a powdery solid product, namely a micromolecular flame retardant (PDL) containing phosphorus-nitrogen flame retardant elements.
3. Adding 45 parts of dried polyether polyol, 43.5 parts of isophorone diisocyanate, 5.4 parts of 2, 2-dimethylolpropionic acid and 4.5 parts of catalyst dibutyltin dilaurate into a three-neck flask, adding 150 parts of acetone, starting a magnetic stirring and condensing system, controlling the temperature of the system to 80 ℃, reacting for 3 hours, adding 4.8 parts of 1, 4-butanediol, 9.7 parts of PDL and 10 parts of acetone into the three-neck flask, continuously reacting for 5 hours, then adding 3.6 parts of triethylamine, simultaneously cooling to 60 ℃, continuously reacting for 30 minutes at 60 ℃, adding 208 parts of distilled water, continuously reacting for 30 minutes, and finishing the reaction.
4. And (3) pouring the solution prepared by the reaction in the step (3) into a polytetrafluoroethylene plate, standing for 24h, and then drying for 36h at the temperature of 60 ℃ to prepare the halogen-free intrinsic flame-retardant waterborne polyurethane film.
As can be seen from figure 1, the carbon residue amount of the flame retardant after combustion reaches more than fifty percent at 550 ℃, and the higher carbon residue amount indicates that more residues can be generated after the flame retardant waterborne polyurethane material is combusted, so that the surface of the material is covered, the flame retardant can effectively play a role in isolating a combustion source, and a good flame retardant effect is achieved.
Comparative example
The preparation method of the non-bittern polyurethane of the comparative example comprises the following steps:
1. adding 15 parts of dried polyether polyol, 14.5 parts of isophorone diisocyanate, 1.8 parts of 2, 2-dimethylolpropionic acid and 1.5 parts of catalyst dibutyltin dilaurate into a three-neck flask according to mass fraction, adding 100 parts of acetone, starting a magnetic stirring and condensing system, controlling the temperature of the system to 80 ℃, and reacting for 3 hours. Then adding 2.2 parts of 1, 4-butanediol and 5 parts of acetone into the three-neck flask, continuing to react for 3 hours, then adding 1.2 parts of triethylamine, simultaneously cooling to 60 ℃, continuing to react for 30 minutes at 60 ℃, adding 60 parts of distilled water, continuing to react for 30 minutes, and ending the reaction.
2. And (3) pouring the solution prepared by the reaction in the step (1) into a polytetrafluoroethylene plate, standing for 24h, and then drying for 36h at the temperature of 60 ℃ to prepare the halogen-free waterborne polyurethane film.
TABLE 1 flammability resistance of flame-retardant aqueous polyurethane
| Sample (I) | Content of flame retardant (%) | Combustibility |
| Comparative example | 0 | Flammable material |
| Example 1 | 4.2 | Non-combustible |
| Example 2 | 6.1 | Non-combustible |
| Example 3 | 7.1 | Non-combustible |
| Example 4 | 8.7 | Non-combustible |
As can be seen from Table 1, the flame retardant has a certain flame retardance on the waterborne polyurethane, and when the addition amount is 4.2%, the waterborne polyurethane material is incombustible in air, which shows that the prepared flame-retardant waterborne polyurethane has good flame retardance under the condition of less flame retardant.
The invention synthesizes the solid micromolecule halogen-free flame retardant containing phosphorus and nitrogen flame retardant elements, and then introduces the flame retardant with reaction property into a waterborne polyurethane system as a chain extender to prepare the halogen-free intrinsic flame retardant waterborne polyurethane, and substances with flame retardant effect are inserted into a polyurethane hard segment structure in the form of existence of the micromolecules, so that the phosphorus and nitrogen elements with flame retardant effect greatly improve the initial decomposition temperature of the polyurethane material and effectively improve the flame retardant effect of the polyurethane material.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (4)
1. The preparation method of the halogen-free intrinsic flame-retardant waterborne polyurethane film is characterized by comprising the following steps of:
s1, preparing an intermediate product pentaerythritol diphosphonate diphosphoryl dichloride PDD;
s2, preparing a micromolecular flame retardant PDL containing phosphorus-nitrogen flame retardant elements: adding 15-45 parts by mass of PDD prepared by S1 into a three-neck flask, sequentially adding 150-250 parts of chloroform, 11-33 parts of diglycolamine and 10-30 parts of triethylamine into the three-neck flask, maintaining the reaction temperature of the system at 10-15 ℃ in an ice-water bath, reacting for 2-3 h, then heating to 30 ℃, continuing the reaction for 4-5 h, evaporating chloroform after the reaction is finished, washing and purifying the product by using a mixed solvent of acetone and absolute ethyl alcohol, and preparing a white powder powdery solid product, namely the PDL containing the phosphorus-nitrogen flame retardant element;
s3, adding 15-45 parts of dried polyether polyol, 14.5-43.5 parts of isophorone diisocyanate, 1.8-5.4 parts of 2, 2-dimethylolpropionic acid and 1.5-4.5 parts of dibutyltin dilaurate into a three-neck flask, adding 100-150 parts of acetone, starting a magnetic stirring and condensing system, controlling the temperature of the system to 80 ℃, reacting for 3 hours, adding 2.2-6.6 parts of 1, 4-butanediol, 1.44-9.7 parts of PDL and 5-10 parts of acetone into the three-neck flask, continuously reacting for 3-5 hours, then adding 1.2-3.6 parts of triethylamine, simultaneously cooling to 60 ℃, continuously reacting for 30 minutes at 60 ℃, adding 60-208 parts of distilled water, continuously reacting for 30 minutes, and finishing the reaction;
and S4, pouring the solution obtained by the reaction of the S3 into a polytetrafluoroethylene plate, standing for 24 hours, and then drying for 36 hours at the temperature of 60 ℃ to obtain the halogen-free intrinsic flame-retardant waterborne polyurethane film.
2. The method for preparing a halogen-free inherently flame-retardant aqueous polyurethane film according to claim 1, characterized in that: the preparation method of the intermediate product pentaerythritol diphosphonate diphosphoryl chloride of the step S1 is as follows: adding 17-34 parts of pentaerythritol into a three-neck flask with a reflux device and a tail gas treatment device, weighing 115-230 parts of phosphorus oxychloride into the three-neck flask, starting a magnetic stirring and condensing device, starting heating, reacting for 1-2 hours when the system temperature reaches 60 ℃, heating to 105 ℃, continuing to react for 6-8 hours, finishing the reaction, repeatedly washing with dichloromethane and absolute ethyl alcohol, carrying out suction filtration and drying respectively, and obtaining white powder, namely an intermediate product pentaerythritol diphosphonite diphosphoryl chloride (PDD).
3. The method for preparing a halogen-free inherently flame-retardant aqueous polyurethane film according to claim 1, characterized in that: the maximum content of the flame retardant PDL in the halogen-free intrinsic flame-retardant waterborne polyurethane film is 8.7%.
4. The halogen-free inherently flame-retardant aqueous polyurethane obtained by the process as claimed in any of claims 1 to 3.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3978167A (en) * | 1974-01-02 | 1976-08-31 | Michigan Chemical Corporation | Pentaerythritol cyclic diphosphates and diphosphoramidates |
| CN101381444A (en) * | 2008-10-31 | 2009-03-11 | 北京理工大学 | Environment friendly non-halogen reacting phosphorus-nitrogen coordinated fire-retardant aqueous polyurethane and preparation method thereof |
| CN101982603A (en) * | 2010-10-22 | 2011-03-02 | 北京理工大学 | Halogen free phosphorous-nitrogen synergic antiflaming water-soluble polyurethane fabric coating agent and preparation method thereof |
| CN102226314A (en) * | 2011-04-29 | 2011-10-26 | 北京理工大学 | Environmentally-friendly halogen-free reaction type soft and hard segment co-modified flame retardant waterborne polyurethane fabric coating agent and preparation method thereof |
| CN104592475A (en) * | 2015-01-28 | 2015-05-06 | 中国科学技术大学 | Method for preparing flame-retardant waterborne polyurethane containing phosphaphenanthrene and/or phenyl phosphate groups |
| CN108976774A (en) * | 2018-06-27 | 2018-12-11 | 滁州环球聚氨酯科技有限公司 | A kind of high-ductility flame retardant polyurethane composite material |
| CN110078886A (en) * | 2019-05-30 | 2019-08-02 | 中原工学院 | A kind of preparation method of phosphorus-nitrogen extinguishing waterborn polyurethane |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040039085A1 (en) * | 2001-03-27 | 2004-02-26 | Kasowshi Robert Valentine | Acid-methylol compound reaction products for flame resistance |
-
2019
- 2019-08-30 CN CN201910817282.7A patent/CN110483735B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3978167A (en) * | 1974-01-02 | 1976-08-31 | Michigan Chemical Corporation | Pentaerythritol cyclic diphosphates and diphosphoramidates |
| CN101381444A (en) * | 2008-10-31 | 2009-03-11 | 北京理工大学 | Environment friendly non-halogen reacting phosphorus-nitrogen coordinated fire-retardant aqueous polyurethane and preparation method thereof |
| CN101982603A (en) * | 2010-10-22 | 2011-03-02 | 北京理工大学 | Halogen free phosphorous-nitrogen synergic antiflaming water-soluble polyurethane fabric coating agent and preparation method thereof |
| CN102226314A (en) * | 2011-04-29 | 2011-10-26 | 北京理工大学 | Environmentally-friendly halogen-free reaction type soft and hard segment co-modified flame retardant waterborne polyurethane fabric coating agent and preparation method thereof |
| CN104592475A (en) * | 2015-01-28 | 2015-05-06 | 中国科学技术大学 | Method for preparing flame-retardant waterborne polyurethane containing phosphaphenanthrene and/or phenyl phosphate groups |
| CN108976774A (en) * | 2018-06-27 | 2018-12-11 | 滁州环球聚氨酯科技有限公司 | A kind of high-ductility flame retardant polyurethane composite material |
| CN110078886A (en) * | 2019-05-30 | 2019-08-02 | 中原工学院 | A kind of preparation method of phosphorus-nitrogen extinguishing waterborn polyurethane |
Non-Patent Citations (2)
| Title |
|---|
| Synergetic enhancement of mechanical and fire-resistance performance of waterborne polyurethane by introducing two kinds of phosphorus–nitrogen flame retardant;Shuang Wang etc.;《Journal of Colloid and Interface Science》;20181103;第537卷;第197-205页 * |
| Synthesis of a phosphorus- and nitrogen- containing flame retardant and evaluation of its application in waterborne polyurethane;Shuang Wang etc.;《J. APPL. POLYM. SCI.》;20180103;第135卷(第16期);第1-10页 * |
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