CN105440274A - Preparation method of high-functionality and high-flame-retardance polyol - Google Patents
Preparation method of high-functionality and high-flame-retardance polyol Download PDFInfo
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- CN105440274A CN105440274A CN201510078499.2A CN201510078499A CN105440274A CN 105440274 A CN105440274 A CN 105440274A CN 201510078499 A CN201510078499 A CN 201510078499A CN 105440274 A CN105440274 A CN 105440274A
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- polyvalent alcohol
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920005862 polyol Polymers 0.000 title abstract description 13
- 150000003077 polyols Chemical class 0.000 title abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 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 27
- 239000000047 product Substances 0.000 claims abstract description 27
- 239000003063 flame retardant Substances 0.000 claims abstract description 25
- 239000003822 epoxy resin Substances 0.000 claims abstract description 24
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 24
- 239000013067 intermediate product Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000004814 polyurethane Substances 0.000 claims abstract description 8
- 229920002635 polyurethane Polymers 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 74
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 28
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 22
- 238000010792 warming Methods 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 238000009413 insulation Methods 0.000 claims description 15
- 239000000376 reactant Substances 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims description 5
- 229940058015 1,3-butylene glycol Drugs 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- YYQRGCZGSFRBAM-UHFFFAOYSA-N Triclofos Chemical compound OP(O)(=O)OCC(Cl)(Cl)Cl YYQRGCZGSFRBAM-UHFFFAOYSA-N 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 230000005070 ripening Effects 0.000 claims description 4
- 229960001147 triclofos Drugs 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- 150000003752 zinc compounds Chemical class 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 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- NPAIMXWXWPJRES-UHFFFAOYSA-N butyltin(3+) Chemical compound CCCC[Sn+3] NPAIMXWXWPJRES-UHFFFAOYSA-N 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
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 3
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 claims description 3
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 3
- 125000003827 glycol group Chemical group 0.000 claims description 3
- 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 3
- 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 3
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 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
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 2
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims 1
- 229920000570 polyether Polymers 0.000 abstract description 11
- 239000004721 Polyphenylene oxide Substances 0.000 abstract description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract 1
- 229910052698 phosphorus Inorganic materials 0.000 abstract 1
- 239000011574 phosphorus Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 14
- 238000009835 boiling Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 229920005830 Polyurethane Foam Polymers 0.000 description 3
- 239000011496 polyurethane foam Substances 0.000 description 3
- 239000004566 building material Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- -1 first in reactor Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 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
- 238000011056 performance test Methods 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 238000005507 spraying 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
Abstract
The present invention discloses a preparation method of high-functionality and high-flame-retardance polyol. The method comprises the following steps: mixing bromine-containing epoxy resin with dihydric alcohol with a mole ratio of 1: (1.9-3.0), adding a polyurethane catalyst accounting for 0.05%-0.65% of the total mass of raw materials, carrying out heating to 120-240 DEG C for reaction for 1.5-6.5 hours; removing unreacted dihydric alcohol from the obtained mixture under a vacuum condition at 210-235 DEG C; and adding an intermediate product with dihydric alcohol removed into a phosphorus-containing flame retardant with a mass ratio of 15-25%, and carrying out uniform stirring at the temperature of 120 DEG C to obtain the product. The advantages of the method disclosed by the present invention are that: on the basis of common raw materials in the market, a bromine-containing polyether polyol product with high functionality, high strength, and high flame-retardance can be produced with lowered production conditions.
Description
Technical field
The invention belongs to polyurethane foam and manufacture field, particularly relate to a kind of preparation method of high functionality high flame retardant polyvalent alcohol.
Background technology
Along with the raising that country requires for energy-saving building material safety performance, as the building material product of excellent heat-insulating property---polyurethane building heat preservation plate material and spray coating heat preservation material etc., propose new requirement, and the insulation Fire resistances for material proposes higher requirement.Under such condition, raw material for polyurethane heat insulation material it is also proposed new insulation back-fire relief requirement, under existing market condition, there is multiple flame retarding polyether, polyester polyol product, wherein with brominated response type polyether glycol for effect is the most obvious.And for the performance of multiple brominated Contents In Polyether Polyol existing on market and quality all uneven, on the whole all there is following defect: working condition requires high, need High Temperature High Pressure; The functionality of product is low, and its functionality is all starkly lower than 4; The ultimate compression strength of goods is low, and there is the problem of obvious poor dimensional stability in the process of product use.These all constrain range of application and the usage quantity of this series products.For this certain situation, according to the starting material that existing market is conventional, propose can to produce under reducing working condition high functionality, high strength, the E. D rings polyol product of high flame resistance.
Summary of the invention
For solving the problems of the technologies described above, the invention provides a kind of starting material conventional according to existing market, reduce working condition just can produce high functionality, high strength, the E. D rings polyol product of high flame resistance.
For achieving the above object, the present invention is achieved by the following technical solutions.
A preparation method for high functionality high flame retardant polyvalent alcohol, comprises the steps:
(1) brominated epoxy resin is mixed for 1:1.9 ~ 3.0 in molar ratio with dibasic alcohol, add the catalysts for polyurethanes accounting for both brominated epoxy resin and dibasic alcohol total mass 0.5 ‰ ~ 0.65%, be heated to 120 ~ 240 DEG C of reactions 1.5 ~ 6.5 hours, be obtained by reacting the mixture that intermediate product and excess glycol form;
(2) mixture that step (1) obtains is removed excessive dibasic alcohol under 210 ~ 235 DEG C of vacuum conditions;
(3) step (2) is removed the phosphonium flame retardant adding intermediate product quality 15 ~ 25% in the intermediate product of excessive dibasic alcohol, stirring at 70 ~ 120 DEG C both obtains product.
In described step (1), first in reactor, be filled with nitrogen protection before heating.Adopt nitrogen protection reactant, can not at high temperature oxidized and variable color.
First be heated to after 120 ~ 130 DEG C of stirrings make reactant be uniformly distributed in described step (1), then be warming up to 180 DEG C of insulations 1 hour, be then warming up to 200 ~ 215 DEG C of backflows 0.5 hour, be finally warming up to 240 DEG C of return ripenings 2 ~ 5 hours; Reactant reaction is carried out thoroughly.
Described in step (1), brominated epoxy resin is
r represents
x in structure above is one or more in Br, Cl, H, simultaneously at least containing a Br.Market can be selected the epoxy resin comprising high bromine content, the resin as following producer and model: the brominated epoxy resin such as South Asia epoxy resin NPEB-340, NPEB-400, NPEB-408, NPEB-450, NPEB-460; The brominated epoxy resins such as China LanXing group epoxy resin EX-48, EX-17.
Dibasic alcohol described in step (1) is one or more in 1,2-PD, 1,3-PD, dipropylene glycol, ethylene glycol, Diethylene Glycol, 1,3 butylene glycol, BDO.Preferential 1,2-PD, 1,3 butylene glycol, ethylene glycol, Diethylene Glycol; The general structure of described dibasic alcohol:
or
Catalysts for polyurethanes described in step (1) is the one in organic titanate class catalyzer, organic tin catalyzer, calcium containing compound, zinc compound.Described organic titanate class catalyzer is one or more in isopropyl titanate, butyl (tetra) titanate; Organic tin catalyzer is the one in Dibutyltin oxide (DBTO), Mono-n-butyltin (MBTO), dibutyl tin laurate (AIRPRODUCTT-12), stannous octoate (AIRPRODUCTT-9); Calcium containing compound is calcium oxide; Zinc compound is the one in zinc oxide, zinc acetate.
In described step (2), vacuum tightness is-0.098 ~-0.095MPa.
Phosphonium flame retardant described in step (3) is one or more in triethyl phosphate (TEP), tricresyl phosphate (2-chloropropyl) ester (TCPP), trichloroethyl phosphate (TCEP), dimethyl methyl phosphonate (DMMP).
Net reaction of the present invention is:
Beneficial effect: compared with prior art, the invention has the advantages that:
1) reduce working condition requirement, under normal pressure, can Reactive Synthesis be completed;
2) improve functionality to 4.1 ~ 4.5 of product;
3) improve the ultimate compression strength of product to more than 200KPa;
4) improve the dimensional stability of product.
Embodiment
In the present invention, a kind of preparation method of high functionality high flame retardant polyvalent alcohol, comprises the steps:
(1) brominated epoxy resin is mixed for 1:1.9 ~ 3.0 in molar ratio with dibasic alcohol, add the catalysts for polyurethanes accounting for both brominated epoxy resin and dibasic alcohol total mass 0.5 ‰ ~ 0.65%, first in reactor, be filled with nitrogen protection, reheat after reactant being uniformly distributed to 120 ~ 130 DEG C of stirrings, be warming up to 180 DEG C of insulations 1 hour again, then 200 ~ 215 DEG C of backflows 0.5 hour is warming up to, finally be warming up to 240 DEG C of return ripenings 2 ~ 5 hours, be obtained by reacting the mixture that intermediate product and excess glycol form;
Described brominated epoxy resin is
wherein R representative
x in structure above is one or more in Br, Cl, H, simultaneously at least containing a Br.
(2) mixture that step (1) obtains is removed excessive dibasic alcohol under 210 ~ 235 DEG C of vacuum conditions;
(3) step (2) is removed the phosphonium flame retardant adding intermediate product quality 15 ~ 25% in the intermediate product of excessive dibasic alcohol, stir at 70 ~ 120 DEG C and obtain product.
Below in conjunction with specific embodiment, the present invention is described in further detail.
In following examples, described brominated epoxy resin all adopts commercially available product, and can be South Epoxy Resin's South Asia epoxy resin brominated species, the trade mark be NPEB-340, NPEB-400, NPEB-450, NPEB-460; China LanXing group blue star epoxy resin brominated species, the trade mark is the one in EX-48.
Embodiment 1:
558.8g epoxy resin NPEB-340 (epoxy group content is 370.5g/eq) is added in 1000ml four-hole boiling flask, 228.3g1, 2-propylene glycol (mol ratio of epoxy and propylene glycol is 1:2.0) and 0.6g dibutyl tin laurate catalyzer, first in reactor, nitrogen protection is filled with, then after utilizing heating jacket slow temperature reaction still to 120 DEG C, open after stirring, after making the equally distributed state of reactant, progressively be warming up to 180 DEG C and be incubated 1 hour, in 200 DEG C of insulation backflows 0.5 hour, after be warming up to 240 DEG C of insulation backflows after 4.0 hours, the oxirane value content of resin cannot be detected, reactant cools to 210 DEG C, excessive propylene glycol is extracted under the condition of vacuum tightness-0.095MPa, to being finally extracted as end without material from reaction system, to obtain low-boiling point material weight be the weight of 112.6g (this value is close to the theoretical value of excessive propylene glycol) and intermediate product is 673.6, last under 120 DEG C of conditions, add after 168.0gTEP mixes, obtain light yellow clear liquid.Described light yellow clear liquid is high functionality high flame retardant polyvalent alcohol, its product performance index: hydroxyl value 200.3mgKOH/g, and viscosity (25 DEG C) is 3000mPa.s, and main body polyethers average functionality is the polyol product of 4.15.
Embodiment 2:
596.0g epoxy resin EX-48 (epoxy group content is 372.5g/eq) is added in 1000ml four-hole boiling flask, 274.0g1, 3-butyleneglycol (1:1.9 of epoxy and propylene glycol) and 0.3gDBTO catalyzer, first in reactor, nitrogen protection is filled with, again in the slow temperature reaction still of sharp heating jacket after material to 120 DEG C, then open after making the equally distributed state of reactant after stirring, progressively be warming up to 180 DEG C of insulations 1 hour again, 215 DEG C are incubated backflow 0.5 hour, after be warming up to 240 DEG C of insulation return ripenings after 4.5 hours, the oxirane value content of resin cannot be detected, reactant cools to 215 DEG C, excessive 1 is extracted under the condition of vacuum tightness-0.095MPa, 3-butyleneglycol, to being finally extracted as end without material from reaction system, obtaining low-boiling point material weight is respectively 132.5g (this value is close to the theoretical value of excess butanediol) and intermediate product weight 736.1g, last under 100 DEG C of conditions, add after 156.4gTCPP/TCEP (mass ratio is 7:3) mixes in intermediate product, obtain light yellow clear liquid.Described light yellow clear liquid is high functionality high flame retardant polyvalent alcohol, its product performance index: hydroxyl value 195.6mgKOH/g, and viscosity (25 DEG C) is 9400mPa.s, and main body polyethers average functionality is 4.15 polyol product.
Embodiment 3:
534.3g epoxy resin NPEB-400 (epoxy group content is 356.2g/eq) is added in 1000ml four-hole boiling flask, 279.4g ethylene glycol (mol ratio of epoxy and propylene glycol is 1:3.0) and 4.0g zinc acetate catalyst, first in reactor, nitrogen protection is filled with, after being slowly warming up to 120 DEG C by heating jacket again, open under stirring the rear equally distributed state of reactant, progressively be warming up to 180 DEG C of insulations 1 hour, 205 DEG C are incubated backflow 0.5 hour, after be warming up to 240 DEG C of insulation backflows after 5.0 hours, the oxirane value content of resin cannot be detected; Reactant cools to 210 DEG C, excessive ethylene glycol is extracted under the condition of vacuum tightness-0.097MPa, to being finally extracted as end without material from reaction system, to obtain low-boiling point material weight be 182.5g (this value is close to the theoretical value of excessive ethylene glycol) and intermediate product weight is 633.8g; Last under 70 DEG C of conditions, add after 126.2gTEP mixes in intermediate product, obtain light yellow clear liquid.Described light yellow clear liquid is high functionality high flame retardant polyvalent alcohol, its product performance index: hydroxyl value 225.7mgKOH/g, and viscosity (25 DEG C) is 6450mPa.s, and main body polyethers average functionality is 4.1 polyol product.
Embodiment 4
530.3g epoxy resin NPEB-400 (epoxy group content is 356.2g/eq) is added in 1000ml four-hole boiling flask, 116.4g ethylene glycol, 142.7g1, 2-propylene glycol (epoxy and dibasic alcohol total amount mol ratio are 1:2.5), and 5.0g zinc acetate catalyst, first in reactor, nitrogen protection is filled with, after being slowly warming up to 120 DEG C by heating jacket again, open under stirring the rear equally distributed state of reactant, progressively be warming up to 180 DEG C of insulations 1 hour, 205 DEG C are incubated backflow 0.5 hour, after be warming up to 240 DEG C of insulation backflows after 2 hours, the oxirane value content of resin cannot be detected, reactant cools to 220 DEG C, excessive mixing glycol is extracted under the condition of vacuum tightness-0.095MPa, to being finally extracted as end without material from reaction system, to obtain low-boiling point material weight be the quality of 149.8g (this value is between excessive ethylene glycol and the theoretical value of propylene glycol) and intermediate product is 637.7g, last under 90 DEG C of conditions, in intermediate product, add 61.2gTEP respectively, after 52.4TCPP mixes, obtain light yellow clear liquid.Described light yellow clear liquid is high functionality high flame retardant polyvalent alcohol, its product performance index: hydroxyl value 230/2mgKOH/g, and viscosity (25 DEG C) is 8650mPa.s, and main body polyethers average functionality is 4.1 polyol product.
Embodiment 5
631.3g epoxy resin NPEB-460 (epoxy group content is 450.9g/eq) is added in 1000ml four-hole boiling flask, 446.5 Diethylene Glycols (epoxy and Diethylene Glycol mol ratio are 1:3), and 5.0g isopropyl titanate, butyl (tetra) titanate (both mass ratio 1:1) catalyzer, first in reactor, nitrogen protection is filled with, after being slowly warming up to 130 DEG C by heating jacket again, open under stirring the rear equally distributed state of reactant, progressively be warming up to 180 DEG C of insulations 1 hour, 205 DEG C are incubated backflow 0.5 hour, after be warming up to 240 DEG C of insulation backflows after 2 hours, the oxirane value content of resin cannot be detected, reactant cools to 235 DEG C, excessive Diethylene Glycol is extracted under the condition of vacuum tightness-0.098MPa, to being finally extracted as end without material from reaction system, to obtain low-boiling point material weight be the weight of 290.6g (this value is close to excessive Diethylene Glycol theoretical value) and intermediate product is 790g, reaction solution is cooled to after 120 DEG C of conditions, adds 58.8gTEP wherein, after 59.7gDMMP mixes, obtain light yellow clear liquid.Described light yellow clear liquid is high functionality high flame retardant polyvalent alcohol, its product performance index: hydroxyl value 170.0mgKOH/g, and viscosity (25 DEG C) is 15600mPa.s, and main body polyethers average functionality is 4.5 polyol product.
The polyurethane foam prepared for brominated flame retardant polyether polyol product 1830 conventional on market carries out comparative tests, and correlated results is as shown in the table:
The hard polyurethane foam formula that table 1 adopts different brominated flame retardant polyether polyols to prepare and the performance test results thereof
Embodiment 6: substantially the same manner as Example 1, difference is: what dibasic alcohol was selected is dipropylene glycol.
Embodiment 7: substantially the same manner as Example 1, difference is: what dibasic alcohol was selected is triethylene glycol.
Embodiment 8: substantially the same manner as Example 1, difference is: what dibasic alcohol was selected is 1,3 butylene glycol.
Embodiment 9: substantially the same manner as Example 1, difference is: what dibasic alcohol was selected is BDO.
Embodiment 10: substantially the same manner as Example 1, difference is: catalyzer is Mono-n-butyltin.
Embodiment 11: substantially the same manner as Example 1, difference is: catalyzer is stannous octoate.
Embodiment 12: substantially the same manner as Example 1, difference is: catalyzer is calcium oxide.
Embodiment 13: substantially the same manner as Example 1, difference is: catalyzer is zinc oxide.
Embodiment 14: substantially the same manner as Example 1, difference is: brominated epoxy resin is NPEB-450.
The present invention is illustrated according to above-described embodiment, should be appreciated that above-described embodiment does not limit the present invention in any form, and all employings are equal to replacement or the technical scheme that obtains of equivalent transformation mode, all drop within protection scope of the present invention.
Claims (10)
1. a preparation method for high functionality high flame retardant polyvalent alcohol, is characterized in that, comprises the steps:
(1) brominated epoxy resin is mixed for 1:1.9 ~ 3.0 in molar ratio with dibasic alcohol, add the catalysts for polyurethanes accounting for both brominated epoxy resin and dibasic alcohol total mass 0.5 ‰ ~ 0.65%, be heated to 120 ~ 240 DEG C of reactions 1.5 ~ 6.5 hours, be obtained by reacting the mixture that intermediate product and excess glycol form;
(2) mixture that step (1) obtains is removed excessive dibasic alcohol under 210 ~ 235 DEG C of vacuum conditions;
(3) step (2) is removed the phosphonium flame retardant adding intermediate product quality 15 ~ 25% in the intermediate product of excessive dibasic alcohol, stir at 70 ~ 120 DEG C and obtain product.
2. the preparation method of a kind of high functionality high flame retardant polyvalent alcohol according to claim 1, is characterized in that, in described step (1), first in reactor, is filled with nitrogen protection before heating.
3. the preparation method of a kind of high functionality high flame retardant polyvalent alcohol according to claim 1, it is characterized in that, first be heated to after 120 ~ 130 DEG C of stirrings make reactant be uniformly distributed in described step (1), be warming up to 180 DEG C of insulations 1 hour again, then be warming up to 200 ~ 215 DEG C of backflows 0.5 hour, be finally warming up to 240 DEG C of return ripenings 2 ~ 5 hours.
4. the preparation method of a kind of high functionality high flame retardant polyvalent alcohol according to claim 1, it is characterized in that, described in step (1), brominated epoxy resin is
, wherein R representative
,
,
,
,
,
, the X in structure above is one or more in Br, Cl, H, simultaneously at least containing a Br.
5. the preparation method of a kind of high functionality high flame retardant polyvalent alcohol according to claim 1, it is characterized in that, described in step (1), the structural formula of dibasic alcohol is
or
.
6. the preparation method of a kind of high functionality high flame retardant polyvalent alcohol according to claim 1 or 5, it is characterized in that, dibasic alcohol described in step (1), be 1,2-propylene glycol, 1, one or more in ammediol, dipropylene glycol, ethylene glycol, Diethylene Glycol, 1,3 butylene glycol, BDO.
7. the preparation method of a kind of high functionality high flame retardant polyvalent alcohol according to claim 1, it is characterized in that, catalysts for polyurethanes described in step (1) is the one in organic titanate class catalyzer, organic tin catalyzer, calcium containing compound, zinc compound.
8. the preparation method of a kind of high functionality high flame retardant polyvalent alcohol according to claim 7, is characterized in that, described organic titanate class catalyzer is one or more in isopropyl titanate, butyl (tetra) titanate; Organic tin catalyzer is the one in Dibutyltin oxide, Mono-n-butyltin, dibutyl tin laurate, stannous octoate; Calcium containing compound is calcium oxide; Zinc compound is the one in zinc oxide, zinc acetate.
9. the preparation method of a kind of high functionality high flame retardant polyvalent alcohol according to claim 1, is characterized in that, in described step (2), vacuum tightness is-0.098 ~-0.095MPa.
10. the preparation method of a kind of high functionality high flame retardant polyvalent alcohol according to claim 1, it is characterized in that, phosphonium flame retardant described in step (3) is one or more in triethyl phosphate, tricresyl phosphate (2-chloropropyl) ester, trichloroethyl phosphate, dimethyl methyl phosphonate.
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| CN112724367A (en) * | 2021-01-14 | 2021-04-30 | 江苏长顺高分子材料研究院有限公司 | Reactive flame-retardant resin, preparation method and application thereof |
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 |
-
2015
- 2015-02-13 CN CN201510078499.2A patent/CN105440274B/en active Active
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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112724367A (en) * | 2021-01-14 | 2021-04-30 | 江苏长顺高分子材料研究院有限公司 | Reactive flame-retardant resin, preparation method and application thereof |
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