CN114957641B - Flame-retardant polyether polyol and single-component polyurethane foam joint mixture using same as raw material - Google Patents
Flame-retardant polyether polyol and single-component polyurethane foam joint mixture using same as raw material Download PDFInfo
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- CN114957641B CN114957641B CN202210079153.4A CN202210079153A CN114957641B CN 114957641 B CN114957641 B CN 114957641B CN 202210079153 A CN202210079153 A CN 202210079153A CN 114957641 B CN114957641 B CN 114957641B
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- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 72
- 229920000570 polyether Polymers 0.000 title claims abstract description 72
- 239000003063 flame retardant Substances 0.000 title claims abstract description 60
- 229920005862 polyol Polymers 0.000 title claims abstract description 60
- 150000003077 polyols Chemical class 0.000 title claims abstract description 60
- 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 59
- 229920005830 Polyurethane Foam Polymers 0.000 title claims abstract description 26
- 239000011496 polyurethane foam Substances 0.000 title claims abstract description 26
- 239000000203 mixture Substances 0.000 title claims abstract description 16
- 239000002994 raw material Substances 0.000 title claims abstract description 16
- 239000006260 foam Substances 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 13
- 239000000460 chlorine Substances 0.000 claims abstract description 10
- IIODSLBLHKTSMP-UHFFFAOYSA-N 3,4-dibromo-3-chlorobutane-1,2-diol Chemical compound BrC(C(CO)O)(CBr)Cl IIODSLBLHKTSMP-UHFFFAOYSA-N 0.000 claims abstract description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 8
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 8
- 239000003999 initiator Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 7
- 230000018044 dehydration Effects 0.000 claims description 7
- 238000006297 dehydration reaction Methods 0.000 claims description 7
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 7
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 5
- 239000003463 adsorbent Substances 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 239000011499 joint compound Substances 0.000 claims description 5
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000391 magnesium silicate Substances 0.000 claims description 5
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 5
- 235000019792 magnesium silicate Nutrition 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 2
- HOWJQLVNDUGZBI-UHFFFAOYSA-N butane;propane Chemical compound CCC.CCCC HOWJQLVNDUGZBI-UHFFFAOYSA-N 0.000 claims description 2
- 239000003610 charcoal Substances 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000007858 starting material Substances 0.000 claims 1
- 238000005187 foaming Methods 0.000 abstract description 7
- 239000003292 glue Substances 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 7
- 238000009776 industrial production Methods 0.000 abstract description 2
- 231100000053 low toxicity Toxicity 0.000 abstract description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 239000000443 aerosol Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 5
- 239000001294 propane Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- ZMSQJSMSLXVTKN-UHFFFAOYSA-N 4-[2-(2-morpholin-4-ylethoxy)ethyl]morpholine Chemical group C1COCCN1CCOCCN1CCOCC1 ZMSQJSMSLXVTKN-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- GTRSAMFYSUBAGN-UHFFFAOYSA-N tris(2-chloropropyl) phosphate Chemical compound CC(Cl)COP(=O)(OCC(C)Cl)OCC(C)Cl GTRSAMFYSUBAGN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000013008 moisture curing Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009436 residential construction Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2639—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing elements other than oxygen, nitrogen or sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4829—Polyethers containing at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
- C08G18/4845—Polyethers containing oxyethylene units and other oxyalkylene units containing oxypropylene or higher oxyalkylene end groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/2645—Metals or compounds thereof, e.g. salts
- C08G65/2648—Alkali metals or compounds thereof
-
- 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
- C08G2101/00—Manufacture of cellular products
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a flame-retardant polyether polyol which is characterized by comprising raw materials of 3, 4-dibromo-3-chloro-1, 2-butanediol, a catalyst and alkylene oxide. The invention also discloses a preparation method of the single-component polyurethane foam joint mixture taking the single-component polyurethane foam joint mixture as a raw material. The flame-retardant polyether polyol contains bromine and chlorine at the same time, so that the flame-retardant property of the OCF foam prepared by the flame-retardant polyether polyol can be effectively improved. The limited flame-retardant polyether polyol meets the requirements of OCF on low-functionality polyether, low-molecular weight and low-viscosity, and the problems of large OCF residual glue amount, low foaming multiplying power and the like are not caused; the initiator has low toxicity, can be less harmful to workers in industrial production, and has little pollution to the environment. The preparation method of the single-component polyurethane foam joint mixture is simple and convenient for daily use.
Description
Technical Field
The invention relates to the technical field of organic material synthesis, in particular to flame-retardant polyether polyol and a single-component polyurethane foam joint mixture using the same as a raw material.
Background
One-component polyurethane foam caulking (OCF) is a special moisture-curing rigid polyurethane foam system. Polyurethane prepolymer, catalyst, foaming agent and the like are filled in a pressure-resistant aerosol can, and when the material is ejected from the aerosol can, the foam-shaped polyurethane material rapidly expands and is solidified with air or moisture in a contacted matrix to form foam. The solidified foam has excellent performances of joint filling, bonding, sealing, heat insulation, sound insulation and the like, and is widely used for filling and sealing side seams of doors and windows of buildings, expansion joints of members and holes. With the rapid development of national residential construction and the continuous improvement of household conditions, the requirements of people on the quality of the building engineering are increasingly high. As a common building material, the single-component polyurethane foam joint mixture has become a key point for research at home and abroad to improve the flame retardant property of the single-component polyurethane foam joint mixture. The flame retardant effect of the one-component polyurethane foam caulking agent on the market at present is poor, and the majority is in the grade of B3 or B2 (DIN 4102B 1). There are two methods for improving the flame retardant properties of single component polyurethane foam caulking agents: 1. flame retardants are added such as tris (2-chloroethyl) phosphate (TCEP), tris (2-chloropropyl) phosphate (TCPP), dimethyl methylphosphonate (DMMP), chlorinated paraffins, and the like. The flame retardant can effectively improve the flame retardant property of the OCF, but at the same time, the problems of increased plasticity, poor adhesive force, splashing during foam ejection and the like of the OCF foam can be caused. 2. Flame retardant polyether polyols are used. Flame retardant elements such as chlorine, bromine, nitrogen, phosphorus and the like are introduced into the polyether polyol. The method has little influence on the mechanical property of the foam and long time for maintaining the flame retardant effect, and has become an important method for improving the flame retardant property of the OCF.
For example, chinese patent document CN109306056a mentions a reactive flame retardant polyether polyol for OCF joint compound and a preparation method thereof, and the flame retardant polyether polyol obtained by the method has good flame retardant property and good dimensional stability, but the product prepared by the method has high viscosity (4000-5000 mpa·s), and the application of the reactive flame retardant polyether polyol in OCF can cause problems of large residual glue amount, low tensile bonding strength, brittle foam, low foaming multiplying power and the like.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects of large residual glue amount, poor foam adhesion, brittle foam and low foaming multiplying power caused by large viscosity of the flame-retardant polyether polyol in the existing single-component polyurethane foam joint mixture, and further provide the flame-retardant polyether polyol and the single-component polyurethane foam joint mixture using the flame-retardant polyether polyol as raw materials.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention provides a flame-retardant polyether polyol, which comprises raw materials of 3, 4-dibromo-3-chloro-1, 2-butanediol, a catalyst and alkylene oxide.
Further, the functionality of the flame-retardant polyether polyol is 2, the bromine content is 25-35 wt%, the chlorine content is 6-8 wt%, the hydroxyl value is 200-250 mgKOH/g, and the viscosity at normal temperature is 2700-3200 mPa.s.
Preferably, the molar ratio of 3, 4-dibromo-3-chloro-1, 2-butanediol to alkylene oxide is 1:3-7.
The alkylene oxide is at least one of ethylene oxide, propylene oxide, butylene oxide and epichlorohydrin; and/or the catalyst is at least one of potassium hydroxide, sodium hydroxide or double metal cyanide complex catalyst.
Further, the raw material also comprises a neutralizer and an adsorbent,
the neutralizer is at least one of acetic acid or phosphoric acid; and/or the number of the groups of groups,
the adsorbent is at least one of magnesium silicate, aluminum silicate, activated clay, activated carbon, molecular sieve, diatomite or neutral charcoal.
The invention also provides a preparation method of the flame-retardant polyether polyol, which comprises the following steps:
mixing an initiator with a catalyst, dehydrating, and introducing nitrogen;
adding alkylene oxide, mixing, and performing ring-opening polymerization reaction after full mixing to obtain crude polyether;
and transferring the obtained crude polyether, adding a neutralizing agent, sampling and testing the pH value to meet the requirement, adding an adsorbent for adsorption, and finally dehydrating to obtain the target product.
Further, the method comprises the steps of,
the dehydration temperature is 100-120 ℃ and the dehydration time is 1-3 hours; and/or the number of the groups of groups,
the mixing temperature of the added alkylene oxide is 90-130 ℃, and the pressure is kept to be less than or equal to 0.4MPa; and/or the number of the groups of groups,
the reaction temperature of the ring-opening polymerization reaction is 100-120 ℃ and the reaction time is 3-5 h; and/or the number of the groups of groups,
the neutralization temperature is 85-90 ℃, the pH value after neutralization is 6-8, and the adsorption temperature is 90-110 ℃.
The invention also provides a single-component polyurethane foam joint mixture, and the raw materials comprise the flame-retardant polyether polyol.
Further, the raw materials comprise:
40-60 parts of flame-retardant polyether polyol, 110-135 parts of polyether polyol with 3 functionality of 500-1000 molecular weight, 7-10 parts of catalyst, 5-6 parts of foam stabilizer, 70-80 parts of dimethyl ether, 70-80 parts of propane butane and 360-400 parts of diphenylmethane diisocyanate (MDI).
Preferably, the diphenylmethane diisocyanate has an NCO content of 30-32.5%, a functionality of 2.7, a total Cl content of 2000 or less, a viscosity of 150-250, and optionally PAPI27 of Dow, S5005 of Huntsman and PM200 of Van.
Compared with the prior art, the invention has the following beneficial effects:
(1) The flame-retardant polyether polyol provided by the invention is prepared from raw materials comprising 3, 4-dibromo-3-chloro-1, 2-butanediol, a catalyst and alkylene oxide, contains bromine and chlorine elements at the same time, does not contain rigid structures such as benzene rings and the like, and has low functionality, molecular weight and viscosity.
(2) The invention limits the functionality of the flame-retardant polyether polyol to 2, and meets the requirement of OCF on low-functionality polyether; the molecular weight is 450-550, and the product meets the requirement of OCF on low molecular weight of 2-functionality polyether; the viscosity is 2700 to 3200 mPa.s (25 ℃), and the problems of large OCF residual glue amount, low foaming multiplying power and the like are avoided.
(2) The single-component polyurethane foam joint mixture provided by the invention has good compatibility with the propane and the dimethyl ether, can be stored for a long time after being uniformly mixed with the propane and the dimethyl ether, and meets the requirement of compatibility in OCF.
(4) The prepared flame-retardant polyether polyol has good adhesion.
(5) The initiator of the flame-retardant polyether polyol has low toxicity, can be less harmful to workers in industrial production, and has less environmental pollution.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
In a specific embodiment of the present invention, the 3-functional polyether polyol used is 1000 molecular weight polyether polyol 310 and 500 molecular weight polyether polyol 305, respectively, produced by optimization chemistry, the catalyst is DMDEE available from Henschel, inc., the foam stabilizer is silicone oil produced by optimization chemistry, and the crude MDI is PM-200 available from Wanhua chemistry.
Example 1
The embodiment provides a preparation method of flame-retardant polyether polyol, which comprises the following steps:
(1) 1000g of 3, 4-dibromo-3-chloro-1, 2-butanediol and 5g of potassium hydroxide are put into a reaction kettle, dehydration is carried out for 2 hours at 110 ℃, after the moisture content is detected to be less than or equal to 500ppm, the vacuum in the reaction kettle is broken by nitrogen, and then the gas in the reaction kettle is replaced for 2 times;
(2) 467.7g of ethylene oxide and 205.5g of propylene oxide are introduced into a reaction kettle at a speed of 1g/min for ring-opening polymerization reaction, the pressure in the kettle is kept to be less than or equal to 0.4MPa, and the temperature is controlled at 120 ℃;
(3) After the metered ethylene oxide and propylene oxide are completely introduced, reacting for 4 hours at 110 ℃ to obtain crude polyether;
(4) Transferring the crude polyether into a neutralization kettle, adding 33.5g of 30wt.% phosphoric acid aqueous solution, stirring for 1 hour at 85 ℃, continuously adding 16.7g of magnesium silicate to adsorb for 1 hour after sampling and testing the PH value to meet the requirements, wherein the adsorption operation temperature is 100 ℃, and then removing water until the water content is less than or equal to 500ppm to obtain the target product flame-retardant polyether polyol.
The flame retardant polyether polyol obtained in this example was tested: bromine content was 33wt.%, chlorine content was 7.5wt.%, viscosity was 2950mpa·s (25 ℃), hydroxyl value=240 mgKOH/g.
Example 2
The embodiment provides a preparation method of flame-retardant polyether polyol, which comprises the following steps:
(1) 1000g of 3, 4-dibromo-3-chloro-1, 2-butanediol and 5.3g of potassium hydroxide are put into a reaction kettle, dehydration is carried out for 2 hours at 110 ℃, after the moisture content is less than or equal to 500ppm, the vacuum in the reaction kettle is broken by nitrogen, and then the gas in the reaction kettle is replaced for 2 times;
(2) 779g of ethylene oxide is introduced into a reaction kettle at a speed of 1g/min for ring-opening polymerization reaction, the pressure in the kettle is kept to be less than or equal to 0.4MPa, and the temperature is controlled at 120 ℃;
(3) After the metered ethylene oxide is completely introduced, reacting for 4 hours at 110 ℃ to obtain crude polyether;
(4) Transferring the crude polyether into a neutralization kettle, adding 35.5g of 30wt.% phosphoric acid aqueous solution, stirring for 1 hour at 85 ℃, continuously adding 17.7g of magnesium silicate to adsorb for 1 hour after sampling and testing the PH value to meet the requirements, wherein the adsorption operation temperature is 100 ℃, and then removing water until the water content is less than or equal to 500ppm to obtain the target product flame-retardant polyether polyol.
The flame retardant polyether polyol obtained in this example was tested: bromine content was 32wt.%, chlorine content was 7wt.%, viscosity was 2750 mPa-s (25 ℃), hydroxyl value=245 mgKOH/g.
Example 3
The embodiment provides a preparation method of flame-retardant polyether polyol, which comprises the following steps:
(1) 1000g of 3, 4-dibromo-3-chloro-1, 2-butanediol and 6.3g of potassium hydroxide are put into a reaction kettle, dehydration is carried out for 2 hours at 110 ℃, after the moisture content is less than or equal to 500ppm, the vacuum in the reaction kettle is broken by nitrogen, and then the gas in the reaction kettle is replaced for 2 times;
(2) 780g of ethylene oxide and 329g of propylene oxide are introduced into a reaction kettle at a speed of 1g/min for ring-opening polymerization reaction, the pressure in the kettle is kept to be less than or equal to 0.4MPa, and the temperature is controlled at 120 ℃;
(3) After the metered alkylene oxide is completely introduced, reacting for 4 hours at 110 ℃ to obtain crude polyether;
(4) Transferring the crude polyether into a neutralization kettle, adding 42.2g of 30wt.% phosphoric acid aqueous solution, stirring for 1 hour at 85 ℃, continuously adding 21.1g of magnesium silicate to adsorb for 1 hour after sampling and testing the PH value to meet the requirements, wherein the adsorption operation temperature is 100 ℃, and then removing water until the water content is less than or equal to 500ppm to obtain the target product flame-retardant polyether polyol.
The flame retardant polyether polyol obtained in this example was tested: bromine content was 28.5wt.%, chlorine content was 6.3wt.%, viscosity was 3007 mpa.s (25 ℃), hydroxyl value = 203mgKOH/g.
Example 4
The embodiment provides a single-component polyurethane foam joint mixture, which is prepared by adding 53g of the flame-retardant polyether polyol obtained in the embodiment 1, 84g of polyether polyol 310, 40g of polyether polyol 305, 8g of catalyst DMDEE, 5g of foam stabilizer, 75g of dimethyl ether, 75g of propane and 385g of PM-200 into a 750mL aerosol can, and uniformly shaking.
Example 5
The embodiment provides a single-component polyurethane foam joint mixture, which is prepared by adding 53g of the flame-retardant polyether polyol obtained in the embodiment 2, 75g of polyether polyol 310, 35g of polyether polyol 305, 10g of catalyst DMDEE, 6g of foam stabilizer, 80g of dimethyl ether, 70g of propane and 400g of PM-200 into a 750mL aerosol can, and uniformly shaking.
Example 6
The embodiment provides a single-component polyurethane foam joint mixture, which is prepared by adding 53g of the flame-retardant polyether polyol obtained in the embodiment 3, 85g of polyether polyol 310, 50g of polyether polyol 305, 7g of catalyst DMDEE, 5g of foam stabilizer, 70g of dimethyl ether, 80g of propane and 360g of PM-200 into a 750mL aerosol can, and uniformly shaking.
Comparative example 1
This comparative example provides a one-component polyurethane foam joint compound which differs from example 4 in that a flame retardant polyether polyol raw material is used, and a raw material bromonitro alcohol disclosed in chinese patent document CN112552503a is used in this comparative example.
Comparative example 2
This comparative example provides a one-component polyurethane foam caulking agent which differs from example 4 in that a flame retardant polyether polyol is used, the flame retardant polyether RF3775 of the optimization chemistry used in this comparative example has a molecular weight of only 264, but a viscosity of 20000-30000.
Experimental example
The one-part polyurethane foam joint compounds prepared in examples 4-6 and comparative examples were each subjected to performance testing, wherein,
the thermal conductivity is measured by a thermal conductivity meter.
The oxygen index test method is in accordance with GB/T2406.2-2009.
The residual glue quantity testing method is to weigh and empty the weight of the bottle after glue is sprayed until the glue cannot be sprayed out.
The test method of the foaming multiple comprises the following steps: spraying materials in a mould, weighing the mass (M) of the foam on a balance with the precision of 0.1 after 72 hours, taking five samples on the upper part, the middle part and the lower part of the foam respectively, testing the density rho, and calculating the volume (V) of the foam by an average value f )：
Wherein:
f-foaming multiple;
V f -foam volume in liters (L);
m-foam mass in grams (g);
p-foam density in kilograms per cubic meter (kg/m) 3 )；
V 0 -aerosol canister indicated capacity in liters (L).
The tensile bond strength test method is in accordance with GB/T13477.8.
The test results are shown in Table 1.
TABLE 1 one-part polyurethane foam joint compound Performance test results
As can be seen from the above table, the flame retardant polyether polyols employed in comparative examples 1 and 2, which are different from the present invention, have substantially the same oxygen index but a higher thermal conductivity than the present invention; meanwhile, as the viscosity of the flame-retardant polyether polyol prepared by the invention is low, the residual gum amount and the foaming multiple are obviously superior to those of comparative examples 1 and 2. The invention does not contain rigid structures such as benzene rings and the like, and has excellent bonding strength; meanwhile, the foam is not easy to be brittle, and the phenomenon of slag kneading can not occur.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (8)
1. A flame-retardant polyether polyol is characterized in that raw materials comprise 3, 4-dibromo-3-chloro-1, 2-butanediol, a catalyst and alkylene oxide;
the functionality of the flame-retardant polyether polyol is 2, the bromine content is 25-35 wt%, the chlorine content is 6-8 wt%, the hydroxyl value is 200-250 mgKOH/g, and the viscosity at normal temperature is 2700-3200 mPa.s;
the molar ratio of 3, 4-dibromo-3-chloro-1, 2-butanediol to alkylene oxide is 1:3-7.
2. The flame retardant polyether polyol of claim 1, wherein the alkylene oxide is at least one of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin; and/or the catalyst is at least one of potassium hydroxide, sodium hydroxide or double metal cyanide complex catalyst.
3. Flame retardant polyether polyol according to claim 1 or 2, wherein the raw materials further comprise a neutralizing agent and an adsorbent,
the neutralizer is at least one of acetic acid or phosphoric acid; and/or the number of the groups of groups,
the adsorbent is at least one of magnesium silicate, aluminum silicate, activated clay, activated carbon, molecular sieve, diatomite or neutral charcoal.
4. A method of preparing a flame retardant polyether polyol according to any one of claims 1 to 3, comprising the steps of:
mixing an initiator with a catalyst, dehydrating, and introducing nitrogen;
adding alkylene oxide, mixing, and ring-opening polymerization reaction after full mixing to obtain the flame-retardant polyether polyol.
5. The method according to claim 4, wherein,
the dehydration temperature is 100-120 ℃ and the dehydration time is 1-3 hours; and/or the number of the groups of groups,
the mixing temperature of the added alkylene oxide is 90-130 ℃, and the pressure is kept to be less than or equal to 0.4MPa; and/or the number of the groups of groups,
the reaction temperature of the ring-opening polymerization reaction is 100-120 ℃ and the reaction time is 3-5 h.
6. A one-component polyurethane foam joint compound characterized in that the starting material comprises the flame retardant polyether polyol of any one of claims 1 to 3 or the flame retardant polyether polyol produced by the production process of claim 4 or 5.
7. The one-part polyurethane foam joint mixture according to claim 6, wherein the raw materials comprise, in parts by weight:
40-60 parts of flame-retardant polyether polyol, 110-135 parts of polyether polyol with 3 functionality of 500-1000 molecular weight, 7-10 parts of catalyst, 5-6 parts of foam stabilizer, 70-80 parts of dimethyl ether, 70-80 parts of propane butane and 360-400 parts of diphenylmethane diisocyanate.
8. The one-part polyurethane foam caulking agent according to claim 7, wherein said diphenylmethane diisocyanate has an NCO content of 30 to 32.5%, a functionality of 2.7, a total Cl content of 2000 or less, and a viscosity of 150 to 250.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3988302A (en) * | 1974-05-24 | 1976-10-26 | Texaco Development Corporation | Polyurethanes prepared by reaction of organic polyisocyanate with brominated ester-containing polyols |
| CN102432859A (en) * | 2011-08-24 | 2012-05-02 | 山东蓝星东大化工有限责任公司 | Synthesis method of flexible-foam flame-retardant polyether polyol |
| CN103497322A (en) * | 2013-09-09 | 2014-01-08 | 江苏雅克科技股份有限公司 | Preparation method and application for reaction-type halogen-containing flame-retardant polyether polyol |
| CN110591070A (en) * | 2019-09-25 | 2019-12-20 | 山东一诺威新材料有限公司 | Castor oil-based flame-retardant polyether polyol for polyurethane elastomer and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109467690A (en) * | 2018-09-17 | 2019-03-15 | 佳化化学科技发展（上海）有限公司 | A kind of flame-retardant polyether glycol and its preparation method and application |
-
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- 2022-01-24 CN CN202210079153.4A patent/CN114957641B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3988302A (en) * | 1974-05-24 | 1976-10-26 | Texaco Development Corporation | Polyurethanes prepared by reaction of organic polyisocyanate with brominated ester-containing polyols |
| CN102432859A (en) * | 2011-08-24 | 2012-05-02 | 山东蓝星东大化工有限责任公司 | Synthesis method of flexible-foam flame-retardant polyether polyol |
| CN103497322A (en) * | 2013-09-09 | 2014-01-08 | 江苏雅克科技股份有限公司 | Preparation method and application for reaction-type halogen-containing flame-retardant polyether polyol |
| CN110591070A (en) * | 2019-09-25 | 2019-12-20 | 山东一诺威新材料有限公司 | Castor oil-based flame-retardant polyether polyol for polyurethane elastomer and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| "反应型阻燃聚醚多元醇的合成及应用";徐娜等;《热固性树脂》;第32卷(第4期);20-28 * |
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