CN105440274B - A kind of preparation method of high functionality high fire-retardance polyalcohol - Google Patents
A kind of preparation method of high functionality high fire-retardance polyalcohol Download PDFInfo
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- CN105440274B CN105440274B CN201510078499.2A CN201510078499A CN105440274B CN 105440274 B CN105440274 B CN 105440274B CN 201510078499 A CN201510078499 A CN 201510078499A CN 105440274 B CN105440274 B CN 105440274B
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- retardance
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- dihydric alcohol
- polyalcohol
- high functionality
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- 150000005846 sugar alcohols Polymers 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000047 product Substances 0.000 claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003822 epoxy resin Substances 0.000 claims abstract description 24
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 239000013067 intermediate product Substances 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000004814 polyurethane Substances 0.000 claims abstract description 8
- 229920002635 polyurethane Polymers 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 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 claims abstract description 5
- 239000003063 flame retardant Substances 0.000 claims abstract description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000010792 warming Methods 0.000 claims description 15
- 239000000376 reactant Substances 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- AXPZIVKEZRHGAS-UHFFFAOYSA-N 3-benzyl-5-[(2-nitrophenoxy)methyl]oxolan-2-one Chemical compound [O-][N+](=O)C1=CC=CC=C1OCC1OC(=O)C(CC=2C=CC=CC=2)C1 AXPZIVKEZRHGAS-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 230000005070 ripening Effects 0.000 claims description 4
- 239000012974 tin catalyst Substances 0.000 claims description 4
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
- NPAIMXWXWPJRES-UHFFFAOYSA-N butyltin(3+) Chemical compound CCCC[Sn+3] NPAIMXWXWPJRES-UHFFFAOYSA-N 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 150000003752 zinc compounds Chemical class 0.000 claims description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical group CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims 1
- JXASPPWQHFOWPL-UHFFFAOYSA-N Tamarixin Natural products C1=C(O)C(OC)=CC=C1C1=C(OC2C(C(O)C(O)C(CO)O2)O)C(=O)C2=C(O)C=C(O)C=C2O1 JXASPPWQHFOWPL-UHFFFAOYSA-N 0.000 claims 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 1
- YYQRGCZGSFRBAM-UHFFFAOYSA-N Triclofos Chemical compound OP(O)(=O)OCC(Cl)(Cl)Cl YYQRGCZGSFRBAM-UHFFFAOYSA-N 0.000 claims 1
- 150000004702 methyl esters Chemical class 0.000 claims 1
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 claims 1
- 229960001147 triclofos Drugs 0.000 claims 1
- 229920005862 polyol Polymers 0.000 abstract description 10
- 150000003077 polyols Chemical class 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 5
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 61
- 239000000463 material Substances 0.000 description 14
- 238000009413 insulation Methods 0.000 description 12
- 238000009835 boiling Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 229920000570 polyether Polymers 0.000 description 9
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- 150000002118 epoxides Chemical class 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 229920005830 Polyurethane Foam Polymers 0.000 description 3
- 239000011496 polyurethane foam Substances 0.000 description 3
- 235000013904 zinc acetate Nutrition 0.000 description 3
- 0 Cc1c(*)c(*)c(*)c(*)c1C Chemical compound Cc1c(*)c(*)c(*)c(*)c1C 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical group CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 2
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- GTACSIONMHMRPD-UHFFFAOYSA-N 2-[4-[2-(benzenesulfonamido)ethylsulfanyl]-2,6-difluorophenoxy]acetamide Chemical compound C1=C(F)C(OCC(=O)N)=C(F)C=C1SCCNS(=O)(=O)C1=CC=CC=C1 GTACSIONMHMRPD-UHFFFAOYSA-N 0.000 description 1
- ANHAEBWRQNIPEV-UHFFFAOYSA-N 2-chloroethyl dihydrogen phosphate Chemical compound OP(O)(=O)OCCCl ANHAEBWRQNIPEV-UHFFFAOYSA-N 0.000 description 1
- 101710130081 Aspergillopepsin-1 Proteins 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 102100031007 Cytosolic non-specific dipeptidase Human genes 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical class C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical class [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of preparation method of high functionality high fire-retardance polyalcohol, comprise the following steps：It is 1 in molar ratio by brominated epoxy resin and dihydric alcohol：1.9 ~ 3.0 mixing, add the catalysts for polyurethanes for accounting for raw material gross mass 0.5 ‰ ~ 0.65%, are heated to 120 ~ 240 DEG C and react 1.5 ~ 6.5 hours；Obtained mixture is removed into unreacted dihydric alcohol under 210 ~ 235 DEG C of vacuum conditions；The intermediate product for removing dihydric alcohol is added to the phosphonium flame retardant of mass ratio 15 ~ 25%, is stirred at 120 DEG C and both obtains product.The invention has the advantages that the raw material commonly used according to existing market, reduce working condition with regard to that can produce high functionality, high intensity, high flame resistance E. D rings polyol product.
Description
Technical field
The invention belongs to polyurethane foam manufacturing field, more particularly to a kind of preparation side of high functionality high fire-retardance polyalcohol
Method.
Background technology
With the raising that country requires for energy-saving building material security performance, as the building material product of excellent heat-insulating property ---
Polyurethane building heat preservation plate material and spray coating heat preservation material etc., it is proposed that new requirement, the insulation Fire resistances for material propose
Higher requirement.Under the conditions of such, new insulation back-fire relief requirement is it is also proposed for the raw material of polyurethane heat insulation material, existing
Under some market conditions, there is a variety of flame retarding polyethers, PEPA product, wherein with brominated response type PPG
It is the most obvious for effect.And the performance and quality for the existing a variety of brominated Contents In Polyether Polyols of in the market all it is irregular not
Together, all there is the defects of following on the whole：Working condition requires height, it is necessary to HTHP；The degree of functionality of product is low, its degree of functionality
All it is significantly lower than 4；The compression strength of product is low, and there is obvious poor dimensional stability during product use
Problem.These all constrain the application and usage amount of this kind of product.For this certain situation, commonly used according to existing market
Raw material, it is proposed that reduce working condition under can produce high functionality, high intensity, high flame resistance E. D rings
Polyol product.
The content of the invention
In order to solve the above technical problems, the present invention provides a kind of raw material commonly used according to existing market, production bar is reduced
Part is with regard to that can produce high functionality, high intensity, high flame resistance E. D rings polyol product.
To reach above-mentioned purpose, the present invention is achieved by the following technical solutions.
A kind of preparation method of high functionality high fire-retardance polyalcohol, comprises the following steps：
(1) it is 1 in molar ratio by brominated epoxy resin and dihydric alcohol：1.9~3.0 mixing, addition account for brominated epoxy resin
With the catalysts for polyurethanes of both dihydric alcohols gross mass 0.5 ‰~0.65%, it is small to be heated to 120~240 DEG C of reactions 1.5~6.5
When, reaction obtains the mixture of intermediate product and excess glycol composition；
(2) mixture that step (1) obtains is removed into excessive dihydric alcohol under 210~235 DEG C of vacuum conditions；
(3) step (2) is removed in the intermediate product of excessive dihydric alcohol and adds containing for intermediate product quality 15~25%
Phosphorus fire retardant, stirred at 70~120 DEG C and both obtain product.
In the step (1), nitrogen protection is first filled with into reactor before heating.Reactant is protected using nitrogen, no
It can at high temperature be oxidized and change colour.
After 120~130 DEG C of stirrings are first heated in the step (1) being uniformly distributed reactant, then 180 DEG C of guarantors are warming up to
Temperature 1 hour, then heat to 200~215 DEG C and flow back 0.5 hour, be finally warming up to 240 DEG C of return ripenings 2~5 hours；Make anti-
Thing reaction is answered to carry out thorough.
Brominated epoxy resin is described in step (1)R is represented X in structure above is the one or more in Br, Cl, H, while at least contains a Br.Market
On can select the epoxy resin that includes high bromine content, such as resin of following producer and model:South Asia epoxy resin NPEB-340,
The brominated epoxy resin such as NPEB-400, NPEB-408, NPEB-450, NPEB-460；China LanXing group epoxy resin EX-48,
The brominated epoxy resins such as EX-17.
Dihydric alcohol described in step (1), it is 1,2-PD, 1,3-PD, DPG, ethylene glycol, diethyl two
One or more in alcohol, 1,3-BDO, BDO.Preferential 1,2-PD, 1,3-BDO, ethylene glycol,
Diethylene glycol；The general structure of the dihydric alcohol：Or
Catalysts for polyurethanes described in step (1) is organic titanate class catalyst, organic tin catalyst, calcic chemical combination
One kind in thing, zinc compound.The organic titanate class catalyst is isopropyl titanate, one kind in butyl titanate or several
Kind；Organic tin catalyst is Dibutyltin oxide (DBTO), Mono-n-butyltin (MBTO), dibutyl tin laurate
One kind in (AIRPRODUCT T-12), stannous octoate (AIRPRODUCT T-9)；Calcium containing compound is calcium oxide；Containing zinc impregnation
Compound is one kind in zinc oxide, zinc acetate.
Vacuum is -0.098~-0.095MPa in the step (2).
Phosphonium flame retardant described in step (3) is triethyl phosphate (TEP), tricresyl phosphate (2- chloropropyls) ester (TCPP), three
One or more in chloroethylphosphate (TCEP), dimethyl methyl phosphonate (DMMP).
The present invention net reaction be：
Beneficial effect：Compared with prior art, the advantage of the invention is that：
1) working condition requirement is reduced, reaction synthesis can be completed under normal pressure；
2) degree of functionality of product is improved to 4.1~4.5；
3) compression strength of product is improved to more than 200KPa；
4) dimensional stability of product is improved.
Embodiment
In the present invention, a kind of preparation method of high functionality high fire-retardance polyalcohol, comprise the following steps：
(1) it is 1 in molar ratio by brominated epoxy resin and dihydric alcohol：1.9~3.0 mixing, addition account for brominated epoxy resin
With the catalysts for polyurethanes of both dihydric alcohols gross mass 0.5 ‰~0.65%, nitrogen protection is first filled with into reactor, is reheated
After being uniformly distributed reactant to 120~130 DEG C of stirrings, then it is warming up to 180 DEG C and is incubated 1 hour, then heats to 200~215
DEG C backflow 0.5 hour, is finally warming up to 240 DEG C of return ripenings 2~5 hours, reaction obtains intermediate product and excess glycol group
Into mixture；
The brominated epoxy resin isWherein R is represented X in structure above is the one or more in Br, Cl, H, while at least contains a Br.
(2) mixture that step (1) obtains is removed into excessive dihydric alcohol under 210~235 DEG C of vacuum conditions；
(3) step (2) is removed in the intermediate product of excessive dihydric alcohol and adds containing for intermediate product quality 15~25%
Phosphorus fire retardant, stirred at 70~120 DEG C and produce product.
With reference to specific embodiment, the present invention is described in further detail.
In following examples, the brominated epoxy resin uses commercially available product, can be South Asia epoxy resin (elder brother
Mountain) Co., Ltd's South Asia epoxy resin brominated species, the trade mark NPEB-340, NPEB-400, NPEB-450, NPEB-460；In
Blue star group of state blue star epoxy resin brominated species, the trade mark are one kind in EX-48.
Embodiment 1：
558.8g epoxy resin NPEB-340 (epoxy group content 370.5g/eq) are added into 1000ml four-hole boiling flasks,
(mol ratio of epoxy and propane diols is 1 to 228.3g1,2- propane diols：2.0) and 0.6g dibutyl tin laurate catalyst, first
Nitrogen is filled with into reactor to be protected, then using the slow temperature reaction kettle of heating mantle to after 120 DEG C, after opening stirring,
After making the equally distributed state of reactant, progressively it is warming up to 180 DEG C and is incubated 1 hour, is flowed back 0.5 hour in 200 DEG C of insulations, after
After being warming up to 240 DEG C of insulation backflows 4.0 hours, the epoxide number content of resin can not be detected；Reactant cools to 210 DEG C, true
Excessive propane diols is extracted under conditions of reciprocal of duty cycle -0.095MPa, to finally being extracted as terminating from reaction system without material, is obtained
To low-boiling point material weight be 112.6g (value is close to the theoretical value of excessive propane diols) and the weight of intermediate product is
673.6；Finally under the conditions of 120 DEG C, after addition 168.0g TEP are well mixed, light yellow clear liquid is produced.It is described pale yellow
Color transparency liquid is high functionality high fire-retardance polyalcohol, its product performance index：Hydroxyl value 200.3mgKOH/g, viscosity (25 DEG C)
For 3000mPa.s, main body polyethers average functionality is 4.15 polyol product.
Embodiment 2：
596.0g epoxy resin EX-48 (epoxy group content 372.5g/eq) are added into 1000ml four-hole boiling flasks,
274.0g1,3- butanediol (the 1 of epoxy and propane diols：1.9) nitrogen and 0.3gDBTO catalyst, is filled with into reactor first
Protected, then material makes reactant uniformly divide to after after 120 DEG C, being then turned on stirring in the slow temperature reaction kettle of sharp heating mantle
After the state of cloth, then be progressively warming up to 180 DEG C be incubated 1 hour, 215 DEG C insulation backflow 0.5 hour, after be warming up to 240 DEG C of insulations
After return ripening 4.5 hours, the epoxide number content of resin can not be detected；Reactant cools to 215 DEG C, vacuum-
Excessive 1,3-BDO is extracted under conditions of 0.095MPa, to finally being extracted as terminating from reaction system without material, point
It is 132.5g (theoretical value of the value close to excess butanediol) and intermediate product weight not obtain low-boiling point material weight
736.1g；Finally under the conditions of 100 DEG C, 156.4g TCPP/TCEP (mass ratioes 7 are added into intermediate product：3) mixing is equal
After even, light yellow clear liquid is produced.The light yellow clear liquid is high functionality high fire-retardance polyalcohol, its properties of product
Index：Hydroxyl value 195.6mgKOH/g, viscosity (25 DEG C) are 9400mPa.s, and main body polyethers average functionality produces for 4.15 polyalcohols
Product.
Embodiment 3：
534.3g epoxy resin NPEB-400 (epoxy group content 356.2g/eq) are added into 1000ml four-hole boiling flasks,
(mol ratio of epoxy and propane diols is 1 to 279.4g ethylene glycol：3.0) and 4.0g zinc acetate catalysts, filled first into reactor
Enter nitrogen protection, then after being to slowly warm up to 120 DEG C by heating mantle, open in the state of reactant after stirring is uniformly distributed, by
Step be warming up to 180 DEG C be incubated 1 hour, 205 DEG C insulation backflow 0.5 hour, after be warming up to 240 DEG C insulation backflow 5.0 hours after, nothing
Method detects the epoxide number content of resin；Reactant cools to 210 DEG C, and excess is extracted under conditions of vacuum -0.097MPa
Ethylene glycol, to finally being extracted as terminating from reaction system without material, obtaining low-boiling point material weight, (value connects for 182.5g
The theoretical value of nearly excessive ethylene glycol) and intermediate product weight be 633.8g；Finally under the conditions of 70 DEG C, added into intermediate product
After 126.2g TEP are well mixed, light yellow clear liquid is produced.The light yellow clear liquid is high functionality high fire-retardance
Polyalcohol, its product performance index：Hydroxyl value 225.7mgKOH/g, viscosity (25 DEG C) are 6450mPa.s, the average function of main body polyethers
Spend for 4.1 polyol products.
Embodiment 4
530.3g epoxy resin NPEB-400 (epoxy group content 356.2g/eq) are added into 1000ml four-hole boiling flasks,
116.4g ethylene glycol, 142.7g1, (epoxy is 1 with dihydric alcohol total amount mol ratio to 2- propane diols：2.5), and 5.0g zinc acetates are urged
Agent, nitrogen protection is filled with into reactor first, then after being to slowly warm up to 120 DEG C by heating mantle, is reacted after opening stirring
In the state of thing is uniformly distributed, be progressively warming up to 180 DEG C be incubated 1 hour, 205 DEG C insulation backflow 0.5 hour, after be warming up to 240
After DEG C insulation backflow 2 hours, the epoxide number content of resin can not be detected；Reactant cools to 220 DEG C, vacuum-
Excessive mixing glycol is extracted under conditions of 0.095MPa, to finally being extracted as terminating from reaction system without material, is obtained
Low-boiling point material weight is the matter of 149.8g (value is between excessive ethylene glycol and the theoretical value of propane diols) and intermediate product
Measure as 637.7g；Finally under the conditions of 90 DEG C, 61.2g TEP are separately added into intermediate product, after 52.4TCPP is well mixed,
Produce light yellow clear liquid.The light yellow clear liquid is high functionality high fire-retardance polyalcohol, its product performance index：
Hydroxyl value 230/2mgKOH/g, viscosity (25 DEG C) are 8650mPa.s, and main body polyethers average functionality is 4.1 polyol products.
Embodiment 5
631.3g epoxy resin NPEB-460 (epoxy group content 450.9g/eq) are added into 1000ml four-hole boiling flasks,
(epoxy is 1 with diethylene glycol mol ratio to 446.5 diethylene glycols：, and 5.0g isopropyl titanates, butyl titanate (both mass ratioes 3)
1：1) catalyst, nitrogen protection is filled with into reactor first, then after being to slowly warm up to 130 DEG C by heating mantle, opens stirring
In the state of reactant is uniformly distributed afterwards, progressively it is warming up to 180 DEG C and is incubated 1 hour, 205 DEG C of insulations flows back 0.5 hour, rear heating
After being flowed back 2 hours to 240 DEG C of insulations, the epoxide number content of resin can not be detected；Reactant cools to 235 DEG C, vacuum-
Excessive diethylene glycol is extracted under conditions of 0.098MPa, to finally being extracted as terminating from reaction system without material, is obtained
Low-boiling point material weight is 290.6g (diethylene glycol theoretical value of the value close to excess) and the weight of intermediate product is 790g；Will
Reaction solution is cooled to after 120 DEG C of conditions, is added 58.8g TEP thereto, after 59.7gDMMP is well mixed, is produced light yellow
Transparency liquid.The light yellow clear liquid is high functionality high fire-retardance polyalcohol, its product performance index：Hydroxyl value
170.0mgKOH/g, viscosity (25 DEG C) are 15600mPa.s, and main body polyethers average functionality is 4.5 polyol products.
The polyurethane foam prepared for the brominated flame retardant polyether polyol product 1830 that in the market is commonly used carries out comparative
Experiment, correlated results are as shown in the table：
The hard polyurethane foam formula and its performance test results that table 1 is prepared using different brominated flame retardant polyether polyols
Embodiment 6：It is substantially the same manner as Example 1, except that：What dihydric alcohol was selected is DPG.
Embodiment 7：It is substantially the same manner as Example 1, except that：What dihydric alcohol was selected is triethylene glycol.
Embodiment 8：It is substantially the same manner as Example 1, except that：What dihydric alcohol was selected is 1,3-BDO.
Embodiment 9：It is substantially the same manner as Example 1, except that：What dihydric alcohol was selected is BDO.
Embodiment 10：It is substantially the same manner as Example 1, except that：Catalyst is Mono-n-butyltin.
Embodiment 11：It is substantially the same manner as Example 1, except that：Catalyst is stannous octoate.
Embodiment 12：It is substantially the same manner as Example 1, except that：Catalyst is calcium oxide.
Embodiment 13：It is substantially the same manner as Example 1, except that：Catalyst is zinc oxide.
Embodiment 14：It is substantially the same manner as Example 1, except that：Brominated epoxy resin is NPEB-450.
The present invention is illustrated according to above-described embodiment, it will be appreciated that above-described embodiment does not limit this in any form
Invention, all technical schemes obtained using equivalent substitution or equivalent transformation mode, is within the scope of the present invention.
Claims (6)
1. a kind of preparation method of high functionality high fire-retardance polyalcohol, it is characterised in that comprise the following steps：
（1）It is 1 in molar ratio by brominated epoxy resin and dihydric alcohol：1.9 ~ 3.0 mixing, addition account for brominated epoxy resin and binary
The catalysts for polyurethanes of both alcohol gross mass 0.5 ‰ ~ 0.65%, it is heated to 120 ~ 240 DEG C and reacts 1.5 ~ 6.5 hours, reaction obtains
The mixture of intermediate product and excess glycol composition；The brominated epoxy resin is,
Wherein R is represented、、、、、, the X in structure above is
One or more in Br, Cl, H, while at least contain a Br；The structural formula of the dihydric alcohol isOr；The catalysts for polyurethanes is organic titanate class catalyst, organic tin catalyst, calcium containing compound, contained
One kind in zinc compound；The dihydric alcohol is 1,2-PD, 1,3-PD, DPG, ethylene glycol, diethyl two
One or more in alcohol, 1,3-BDO, BDO；
（2）By step（1）Obtained mixture removes excessive dihydric alcohol under 210 ~ 235 DEG C of vacuum conditions；
（3）By step（2）Remove the phosphor-containing flame-proof that intermediate product quality 15 ~ 25% is added in the intermediate product of excessive dihydric alcohol
Agent, stirred at 70 ~ 120 DEG C and produce product.
A kind of 2. preparation method of high functionality high fire-retardance polyalcohol according to claim 1, it is characterised in that the step
Suddenly（1）In, nitrogen protection is first filled with into reactor before heating.
A kind of 3. preparation method of high functionality high fire-retardance polyalcohol according to claim 1, it is characterised in that the step
Suddenly（1）It is middle be first heated to 120 ~ 130 DEG C stirring be uniformly distributed reactant after, then be warming up to 180 DEG C be incubated 1 hour, Ran Housheng
Temperature flows back 0.5 hour to 200 ~ 215 DEG C, is finally warming up to 240 DEG C of return ripenings 2 ~ 5 hours.
4. the preparation method of a kind of high functionality high fire-retardance polyalcohol according to claim 1, it is characterised in that described to have
Organic titanate class catalyst is the one or more in isopropyl titanate, butyl titanate；Organic tin catalyst is dibutyl oxygen
Change one kind in tin, Mono-n-butyltin, dibutyl tin laurate, stannous octoate；Calcium containing compound is calcium oxide；Closed containing zinc impregnation
Thing is one kind in zinc oxide, zinc acetate.
A kind of 5. preparation method of high functionality high fire-retardance polyalcohol according to claim 1, it is characterised in that the step
Suddenly（2）Middle vacuum is -0.098 ~ -0.095MPa.
A kind of 6. preparation method of high functionality high fire-retardance polyalcohol according to claim 1, it is characterised in that step
（3）Described in phosphonium flame retardant be triethyl phosphate, tricresyl phosphate（2- chloropropyls）Ester, trichloroethyl phosphate, methylphosphonic acid two
One or more in methyl esters.
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Citations (4)
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|---|---|---|---|---|
| US4316991A (en) * | 1980-09-02 | 1982-02-23 | Texaco Inc. | Modification of polyols with epoxy resins |
| EP0265225A2 (en) * | 1986-10-23 | 1988-04-27 | ARCO Chemical Technology, L.P. | Packaging foam polyurethane composition employing epoxy resin modified polyether polyols |
| CN101824133A (en) * | 2010-04-28 | 2010-09-08 | 天津大学 | Preparation method for waterborne polyurethane modified epoxy resin curing agent |
| CN103265679A (en) * | 2013-05-15 | 2013-08-28 | 陕西煤业化工技术研究院有限责任公司 | Epoxy modified polyurethane composition for coal stratum reinforcement and preparation method thereof |
-
2015
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4316991A (en) * | 1980-09-02 | 1982-02-23 | Texaco Inc. | Modification of polyols with epoxy resins |
| EP0265225A2 (en) * | 1986-10-23 | 1988-04-27 | ARCO Chemical Technology, L.P. | Packaging foam polyurethane composition employing epoxy resin modified polyether polyols |
| CN101824133A (en) * | 2010-04-28 | 2010-09-08 | 天津大学 | Preparation method for waterborne polyurethane modified epoxy resin curing agent |
| CN103265679A (en) * | 2013-05-15 | 2013-08-28 | 陕西煤业化工技术研究院有限责任公司 | Epoxy modified polyurethane composition for coal stratum reinforcement and preparation method thereof |
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