CN105295018A - Modified cardanol-based polyether polyol and high-fire-resistant hard polyurethane foam prepared by modified cardanol-based polyether polyol and preparation method thereof - Google Patents
Modified cardanol-based polyether polyol and high-fire-resistant hard polyurethane foam prepared by modified cardanol-based polyether polyol and preparation method thereof Download PDFInfo
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- CN105295018A CN105295018A CN201510798040.XA CN201510798040A CN105295018A CN 105295018 A CN105295018 A CN 105295018A CN 201510798040 A CN201510798040 A CN 201510798040A CN 105295018 A CN105295018 A CN 105295018A
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- 229920000570 polyether Polymers 0.000 title claims abstract description 56
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 48
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical class OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 title claims abstract description 47
- 229920005862 polyol Polymers 0.000 title claims abstract description 17
- 150000003077 polyols Chemical class 0.000 title claims abstract description 17
- 229920005830 Polyurethane Foam Polymers 0.000 title claims abstract description 12
- 239000011496 polyurethane foam Substances 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 238000004917 polyol method Methods 0.000 title 1
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 claims abstract description 43
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims abstract description 43
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims abstract description 43
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims abstract description 43
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 15
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 15
- 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 group 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 14
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 14
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 13
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims abstract description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 36
- 230000004048 modification Effects 0.000 claims description 27
- 238000012986 modification Methods 0.000 claims description 27
- 239000003063 flame retardant Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000006260 foam Substances 0.000 claims description 18
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 18
- 238000010792 warming Methods 0.000 claims description 18
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 14
- ICBQXEWYZVQCFH-UHFFFAOYSA-N 3-(4-bromoanilino)-n,n-dimethylpropanamide Chemical compound CN(C)C(=O)CCNC1=CC=C(Br)C=C1 ICBQXEWYZVQCFH-UHFFFAOYSA-N 0.000 claims description 13
- 229950001336 bromamide Drugs 0.000 claims description 13
- 238000009413 insulation Methods 0.000 claims description 11
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 230000006837 decompression Effects 0.000 claims description 9
- 230000018044 dehydration Effects 0.000 claims description 9
- 238000006297 dehydration reaction Methods 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 239000003381 stabilizer Substances 0.000 claims description 8
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 7
- 238000010907 mechanical stirring Methods 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229920005906 polyester polyol Polymers 0.000 claims description 7
- 229920001228 polyisocyanate Polymers 0.000 claims description 7
- 239000005056 polyisocyanate Substances 0.000 claims description 7
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 244000226021 Anacardium occidentale Species 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 235000020226 cashew nut Nutrition 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 6
- 150000004703 alkoxides Chemical class 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- -1 propylene oxide alkoxide Chemical class 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 229920000877 Melamine resin Polymers 0.000 abstract description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 abstract description 2
- GVPODVKBTHCGFU-UHFFFAOYSA-N 2,4,6-tribromoaniline Chemical compound NC1=C(Br)C=C(Br)C=C1Br GVPODVKBTHCGFU-UHFFFAOYSA-N 0.000 abstract 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 abstract 1
- 239000004088 foaming agent Substances 0.000 abstract 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 abstract 1
- 150000005846 sugar alcohols Polymers 0.000 abstract 1
- 239000000463 material Substances 0.000 description 5
- 230000000979 retarding effect Effects 0.000 description 5
- 239000003999 initiator Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000006683 Mannich reaction Methods 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- VNWKTOKETHGBQD-AKLPVKDBSA-N carbane Chemical compound [15CH4] VNWKTOKETHGBQD-AKLPVKDBSA-N 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 239000012774 insulation material Substances 0.000 description 2
- 150000002829 nitrogen Chemical class 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JHXVRRJXCDAINK-UHFFFAOYSA-N NC(=O)N.N#CC#N Chemical compound NC(=O)N.N#CC#N JHXVRRJXCDAINK-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 206010000269 abscess Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000000640 hydroxylating effect Effects 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a modified cardanol-based polyether polyol and high-fire-resistant hard polyurethane foam prepared by the modified cardanol-based polyether polyol and a preparation method thereof. The polyether polyol takes cardanol, paraformaldehyde, diethanolamine, diethylenetriamine, tribromoaniline, melamine, oxirane and epoxypropane as raw materials, the raw materials are reacted for synthesis of cardanol Mannich polyether polyol, a hydroxyl value is 200-700mg/gKOH, the moisture is less than or equal to 1.0%, the viscosity is 1000-12000 mPa.s (at 25 DEG C), and the cardanol-based polyether polyol can be taken as a polyhydric alcohol component which can be used in the hard polyurethane foam. The product has advantage of adjustable functionality, contains a flame-retardant group, and has good compatibility with a cyclopentane foaming agent.
Description
Technical field
The present invention relates to a kind of modification cardanol based polyether polyol and with its high flame retardant hard polyurethane foams prepared and preparation method thereof.
Background technology
In recent years, the fire disaster caused by architecture exterior wall insulating materials especially rigid polyurethane foam (RPUF) happens occasionally, cause great loss of life and personal injury and property damage, create severe social influence, this seriously constrains the development of polyurethane heat insulation material, and fire-retardant research is extremely urgent." GB8624-2012 material of construction and the product burns grading performance " that come into effect on October 1st, 2013 is inner, explicitly call for for metope insulation foamed plastic, B1 level material must meet limiting oxygen index(LOI) LOI >=30%, and B2 level material must meet LOI >=26%." GB50016-2014 Code for fire protection design of buildings " different fire ratings to architecture exterior wall insulating materials that on May 1st, 2015 formally implements have made specified in more detail (see table 1), for common polyurethane heat insulation material, generally can reach B2 grade standard, be only applicable to lower level building, and for the even A grade standard of the B1 required by middle-high building, this type of polyurethane material that can realize real large-scale application have not been reported.
In urethane, adding fire retardant or in polyether structure, introduce ignition-proof element or structure, is realize two fire-retardant main paties, is called additive flame retardant and structure-type (response type) is fire-retardant.Although it is simpler directly to add fire retardant technique in foaming raw material, cost is also minimum, but there is easily precipitation, affect the defects such as foam monolith performance, and due to the consumption of fire retardant limited, the RPUF of simple interpolation fire retardant generally only can reach about LOI25%, structure-type fire retardant (flame retarding polyether) does not have this misgivings, and it is present in polyurethane structural, can not separate out; Participate in the foamable reaction of urethane, generally do not affect the overall performance of foam; In formula, it even can also be added to 100 parts.In the flame retardant area of RPUF, the flame retarding polyether seeking excellent performance has more potential competitive power.
The gordian technique of flame retarding polyether is the preparation of flame retardant type initiator and the synthesis of polyethers, and the initiator developed at present is based on Halogen system (Br, Cl), phosphorus system and nitrogen series elements, and each series elements system cross development, interpenetrates.Comparatively speaking, nitrogen series elements is due to the low cigarette of low toxicity, and flame retarding efficiency is good and cheap, and world in recent years flame retardant area obtains extensive concern.Containing nitrogen compound as Dyhard RU 100, trimeric cyanamide, cyanogen urea acid trimeric cyanamide etc.; necessarily applied; it has been generally acknowledged that nitrogenous flame ratardant plays multiple flame retardant efficiency at condensed phase and gas phase simultaneously; as heat absorption, generate rare gas element, promote into charcoal, form expansion barrier layer and melting and move heat etc.; fire-retardant mechanism is unique, is consistent with the current requirement of preserving the ecological environment.
At present, at structure-type flame retarding polyether preparing technical field, research emphasis both domestic and external and difficult point are structure design and the synthesis of initiator.
Summary of the invention
The object of this invention is to provide that functionality is adjustable, flame retardant effect be good, well dissolve each other with pentamethylene whipping agent, a kind of modification cardanol based polyether polyol of stable mechanical property and with its high flame retardant hard polyurethane foams prepared and preparation method thereof;
To achieve these goals, technical scheme of the present invention is:
A kind of modification cardanol based polyether polyol, it is characterized in that: after one or both in cardanol, trimeric cyanamide and bromamide, paraformaldehyde mixing, drip in diethanolamine and diethylenetriamine one or both, the mol ratio wherein between cardanol, diethanolamine and/or diethylenetriamine, paraformaldehyde is 1:1 ~ 4:1 ~ 4; Modification cashew nut phenolic group Mannich alkali intermediate is obtained by reacting by Mannich, obtain with oxyethane and propylene oxide alkoxide more further, oxyethane and propylene oxide total mole number are 3 ~ 16 times of cardanol, trimeric cyanamide and/or bromamide total mole number, its viscosity 25 DEG C is 1000-12000mPas, hydroxyl value is 200-700mg/gKOH, moisture≤1%wt; The reaction conditions of obtained modification cashew nut phenolic group Mannich alkali intermediate is 50-120 DEG C, and diethanolamine/triethylene diamine time for adding is 1-2h, and the reaction times is 2-5h; React the water of complete removing reaction system, when water-content is less than 1.0%wt, carry out alkoxide reaction, temperature of reaction is 130-150 DEG C, and the reaction times is 2-6h.
It is characterized in that: on four-necked bottle, load onto reflux condensing tube, 302g cardanol is added in four-necked bottle, paraformaldehyde 72g, trimeric cyanamide 25g stirred under nitrogen atmosphere mixes, be warming up to 80 DEG C, drip diethanolamine 200g, time for adding is 1h, then at 90 DEG C, 4h is reacted, continue to be warming up to 110 DEG C, decompression dehydration makes moisture be less than 1.0%, pass into 80g oxyethane and 162g propylene oxide reaction continuously, temperature controls at about 130 DEG C, still internal pressure remains on 0.4 1 0.6MPa, when pressure cooling is for normal pressure, polyreaction terminates, at 110 DEG C of insulation 2h, vacuumize 30min, obtain modification cardanol Mannich polyether glycol, its hydroxyl value is 470mg/gKOH, 25 DEG C of viscosity are 5500mPas.
It is characterized in that: comprise the following steps: step (1) is on four-necked bottle, load onto reflux condensing tube, 302g cardanol is added in four-necked bottle, paraformaldehyde 72g, bromamide 66g stirred under nitrogen atmosphere mixes, be warming up to 80 DEG C, drip diethanolamine 200g, time for adding is 1h, then at 90 DEG C, 4h is reacted, continue to be warming up to 110 DEG C, decompression dehydration makes moisture be less than 1.0%, pass into 80g oxyethane and 162g propylene oxide reaction continuously, temperature controls at about 130 DEG C, still internal pressure remains on 0.4 ~ 0.6MPa, when pressure cooling is for normal pressure, polyreaction terminates, at 110 DEG C of insulation 2h, vacuumize 30min, obtain modification cardanol Mannich polyether glycol, its hydroxyl value is 402mg/gKOH, 25 DEG C of viscosity are 6500mPas,
Step (2) takes above-mentioned polyether glycol 60g, polyester polyol 40g, foam stabilizer (AK-8805) 3g, amines catalyst (N according to mass parts, N-dimethylcyclohexylamine) 0.76g, metal-based catalysts isocaprylic acid potassium 0.75g, Potassium ethanoate 0.5g, water 1.5g, pentamethylene 15g mixing and stirring be mixed with combined polyether, then in cup, add aforesaid combination polyethers 11.6g, polymethine polyphenyl polyisocyanate 20.1g successively, mechanical stirring 10s under rotating speed 3000-3500r/min condition, obtained urethane foam oxygen index is 32.3%.
It is characterized in that: on four-necked bottle, load onto reflux condensing tube, 302g cardanol is added in four-necked bottle, paraformaldehyde 72g, bromamide 66g stirred under nitrogen atmosphere mixes, be warming up to 80 DEG C, drip diethanolamine 200g, time for adding is 1h, then at 90 DEG C, 4h is reacted, continue to be warming up to 110 DEG C, decompression dehydration makes moisture be less than 1.0%, pass into 80g oxyethane and 162g propylene oxide reaction continuously, temperature controls at about 130 DEG C, still internal pressure remains on 0.4 1 0.6MPa, when pressure cooling is for normal pressure, polyreaction terminates, at 110 DEG C of insulation 2h, vacuumize 30min, obtain modification cardanol Mannich polyether glycol, its hydroxyl value is 402mg/gKOH, 25 DEG C of viscosity are 6500mPas, then above-mentioned polyether glycol 60g, polyester polyol 40g, foam stabilizer (AK-8805) 3g, amines catalyst (N is taken according to mass parts, N-dimethylcyclohexylamine) 0.76g, metal-based catalysts isocaprylic acid potassium 0.75g, Potassium ethanoate 0.5g, water 1.5g, pentamethylene 15g mixing and stirring be mixed with combined polyether, then in cup, add aforesaid combination polyethers 11.6g, polymethine polyphenyl polyisocyanate 20.1g successively, mechanical stirring 10s under rotating speed 3000-3500r/min condition, obtained urethane foam oxygen index is 32.3%.
Further: after cardanol, the mixing of liquefaction trimeric cyanamide, bromamide and paraformaldehyde, drip diethanolamine and diethylenetriamine, modification cashew nut phenolic group Mannich alkali intermediate is obtained by reacting by Mannich, obtain with oxyethane and propylene oxide alkoxide more further, its viscosity 25 DEG C is 1000-12000mPas, hydroxyl value is 200-700mg/gKOH, moisture≤1%wt; Wherein cardanol, diethanolamine or diethylenetriamine and formaldehyde mole ratio are 1:1:1-1:4:4, oxyethane and propylene oxide total mole number are 3-16 times of cardanol, trimeric cyanamide and bromamide total mole number, the reaction conditions of obtained modification cashew nut phenolic group Mannich alkali intermediate is 50-120 DEG C, diethanolamine/triethylene diamine time for adding is 1-2h, and the reaction times is 2-5h; React the water of complete removing reaction system, when water-content is less than 1.0%wt, carry out alkoxide reaction, temperature of reaction is 130-150 DEG C, and the reaction times is 2-6h.By the impact of the factor such as initiator structure, oxyethane, propylene oxide quality in research reaction process on polyether glycol structure and performance, Optimizing Technical.
tool of the present invention has the following advantages:
(1) raw material adopts biological material cardanol to substitute petrochemical material, inexpensive abundant, renewable;
(2) constructional feature of cardanol makes it have a lot of excellent properties, and rigidity benzene ring structure makes cardanol have resistance to elevated temperatures; Between phenyl ring, position can increase the toughness of system containing carbon 15 long alkyl chain of unsaturated carbon-carbon double bond and reduce the viscosity of system;
(3) utilize Mannich to react, structure and the adjustable polyether glycol of functionality can be obtained;
(4) add trimeric cyanamide, bromamide carries out modification, improve polyvalent alcohol nitrogen heterocyclic and bromo element content, improve intrinsic flame-retarding characteristic.Obtained rigid urethane foam abscess is fine and smooth, and good, the fire-retardant rank of mechanical stability is high, high insulating effect;
(5) introduce phenyl ring rigid structure, introduce the ignition-proof elements such as N, Br and make it have excellent mechanics, heat-resisting, flame retardant properties; Between phenyl ring, position is carbon 15 long alkyl chain containing unsaturated carbon-carbon double bond, can be well compatible with pentamethylene whipping agent, can also increase the toughness of system and reduce the viscosity of system.It is characterized in that in Mannich reaction system by adding trimeric cyanamide or bromamide carries out modification, obtained polyether glycol is containing ignition-proof elements such as N, Br, it is characterized in that passing through hydroxylating, liquefaction trimeric cyanamide, and the H activated in melamine molecule structure, the intermolecular polymerization reaction occurred after adopting Mannich reaction to stop trimeric cyanamide liquefaction, obtains the adjustable trimeric cyanamide Mannich polyvalent alcohol of functionality by changing feed ratio; The application of modification cardanol based polyether polyol in the flame-retardant hard polyurethane foam board preparing pentamethylene foaming system.Modification cardanol based polyether polyol, itself and catalyzer, pentamethylene whipping agent, foam stabilizer, fire retardant, water etc. are hybridly prepared into premixed systems, react with the many phenyl isocyanate of polymethine and prepare hard polyurethane foams, isocyanate index 200-400, coordinate modification cardanol based polyether polyol, obtained hard polyurethane foams good flame resistance, stable mechanical property, excellent thermal insulation performance.
Embodiment
Embodiment 1
On four-necked bottle, load onto reflux condensing tube, 302g cardanol is added in four-necked bottle, paraformaldehyde 72g, trimeric cyanamide 25g stirred under nitrogen atmosphere mixes, be warming up to 80 DEG C, drip diethanolamine 200g, time for adding is 1h, then at 90 DEG C, 4h is reacted, continue to be warming up to 110 DEG C, decompression dehydration makes moisture be less than 1.0%, pass into 80g oxyethane and 162g propylene oxide reaction continuously, temperature controls at about 130 DEG C, still internal pressure remains on 0.4 1 0.6MPa, when pressure cooling is for normal pressure, polyreaction terminates, at 110 DEG C of insulation 2h, vacuumize 30min, obtain modification cardanol Mannich polyether glycol, its hydroxyl value is 470mg/gKOH, 25 DEG C of viscosity are 5500mPas.Then according to mass parts take above-mentioned polyether glycol 60g, polyester polyol 40g, foam stabilizer (AK-8805) 3g, amines catalyst (N, N-dimethylcyclohexylamine) 0.76g, metal-based catalysts isocaprylic acid potassium 0.75g, Potassium ethanoate 0.5g, water 1.5g, pentamethylene 15g mixing and stirring be mixed with combined polyether, then in cup, add aforesaid combination polyethers 11.6g, polymethine polyphenyl polyisocyanate 20.9g successively, mechanical stirring 10s under rotating speed 3000-3500r/min condition, obtained urethane foam oxygen index is 31.2%.
Embodiment 2
On four-necked bottle, load onto reflux condensing tube, 302g cardanol is added in four-necked bottle, paraformaldehyde 72g, bromamide 66g stirred under nitrogen atmosphere mixes, be warming up to 80 DEG C, drip diethanolamine 200g, time for adding is 1h, then at 90 DEG C, 4h is reacted, continue to be warming up to 110 DEG C, decompression dehydration makes moisture be less than 1.0%, pass into 80g oxyethane and 162g propylene oxide reaction continuously, temperature controls at about 130 DEG C, still internal pressure remains on 0.4 1 0.6MPa, when pressure cooling is for normal pressure, polyreaction terminates, at 110 DEG C of insulation 2h, vacuumize 30min, obtain modification cardanol Mannich polyether glycol, its hydroxyl value is 402mg/gKOH, 25 DEG C of viscosity are 6500mPas.Then according to mass parts take above-mentioned polyether glycol 60g, polyester polyol 40g, foam stabilizer (AK-8805) 3g, amines catalyst (N, N-dimethylcyclohexylamine) 0.76g, metal-based catalysts isocaprylic acid potassium 0.75g, Potassium ethanoate 0.5g, water 1.5g, pentamethylene 15g mixing and stirring be mixed with combined polyether, then in cup, add aforesaid combination polyethers 11.6g, polymethine polyphenyl polyisocyanate 20.1g successively, mechanical stirring 10s under rotating speed 3000-3500r/min condition, obtained urethane foam oxygen index is 32.3%.
Embodiment 3
On four-necked bottle, load onto reflux condensing tube, 302g cardanol is added in four-necked bottle, paraformaldehyde 72g, trimeric cyanamide 25g stirred under nitrogen atmosphere mixes, be warming up to 80 DEG C, drip diethylenetriamine 230g, time for adding is 2h, then at 90 DEG C, 4h is reacted, continue to be warming up to 110 DEG C, decompression dehydration makes moisture be less than 1.0%, pass into 80g oxyethane and 162g propylene oxide reaction continuously, temperature controls at about 130 DEG C, still internal pressure remains on 0.4 1 0.6MPa, when pressure cooling is for normal pressure, polyreaction terminates, at 110 DEG C of insulation 2h, vacuumize 30min, obtain modification cardanol Mannich polyether glycol, its hydroxyl value is 509mg/gKOH, 25 DEG C of viscosity are 5700mPas.Then according to mass parts take above-mentioned polyether glycol 60g, polyester polyol 40g, foam stabilizer (AK-8805) 3g, amines catalyst (N, N-dimethylcyclohexylamine) 0.76g, metal-based catalysts isocaprylic acid potassium 0.75g, Potassium ethanoate 0.5g, water 1.5g, pentamethylene 15g mixing and stirring be mixed with combined polyether, then in cup, add aforesaid combination polyethers 11.6g, polymethine polyphenyl polyisocyanate 20.9g successively, mechanical stirring 10s under rotating speed 3000-3500r/min condition, obtained urethane foam oxygen index is 31.5%.
Claims (4)
1. a modification cardanol based polyether polyol, it is characterized in that: after one or both in cardanol, trimeric cyanamide and bromamide, paraformaldehyde mixing, drip in diethanolamine and diethylenetriamine one or both, the mol ratio wherein between cardanol, diethanolamine and/or diethylenetriamine, paraformaldehyde is 1:1 ~ 4:1 ~ 4; Modification cashew nut phenolic group Mannich alkali intermediate is obtained by reacting by Mannich, obtain with oxyethane and propylene oxide alkoxide more further, oxyethane and propylene oxide total mole number are 3 ~ 16 times of cardanol, trimeric cyanamide and/or bromamide total mole number, its viscosity 25 DEG C is 1000-12000mPas, hydroxyl value is 200-700mg/gKOH, moisture≤1%wt; The reaction conditions of obtained modification cashew nut phenolic group Mannich alkali intermediate is 50-120 DEG C, and diethanolamine/triethylene diamine time for adding is 1-2h, and the reaction times is 2-5h; React the water of complete removing reaction system, when water-content is less than 1.0%wt, carry out alkoxide reaction, temperature of reaction is 130-150 DEG C, and the reaction times is 2-6h.
2. a kind of modification cardanol based polyether polyol according to claim 1, it is characterized in that: on four-necked bottle, load onto reflux condensing tube, 302g cardanol is added in four-necked bottle, paraformaldehyde 72g, trimeric cyanamide 25g stirred under nitrogen atmosphere mixes, be warming up to 80 DEG C, drip diethanolamine 200g, time for adding is 1h, then at 90 DEG C, 4h is reacted, continue to be warming up to 110 DEG C, decompression dehydration makes moisture be less than 1.0%, pass into 80g oxyethane and 162g propylene oxide reaction continuously, temperature controls at about 130 DEG C, still internal pressure remains on 0.4 1 0.6MPa, when pressure cooling is for normal pressure, polyreaction terminates, at 110 DEG C of insulation 2h, vacuumize 30min, obtain modification cardanol Mannich polyether glycol, its hydroxyl value is 470mg/gKOH, 25 DEG C of viscosity are 5500mPas.
3. high flame retardant hard polyurethane foams prepared by the modification cardanol based polyether polyol described in a right to use 1 ~ 2, it is characterized in that: comprise the following steps: step (1) is on four-necked bottle, load onto reflux condensing tube, 302g cardanol is added in four-necked bottle, paraformaldehyde 72g, bromamide 66g stirred under nitrogen atmosphere mixes, be warming up to 80 DEG C, drip diethanolamine 200g, time for adding is 1h, then at 90 DEG C, 4h is reacted, continue to be warming up to 110 DEG C, decompression dehydration makes moisture be less than 1.0%, pass into 80g oxyethane and 162g propylene oxide reaction continuously, temperature controls at about 130 DEG C, still internal pressure remains on 0.4 ~ 0.6MPa, when pressure cooling is for normal pressure, polyreaction terminates, at 110 DEG C of insulation 2h, vacuumize 30min, obtain modification cardanol Mannich polyether glycol, its hydroxyl value is 402mg/gKOH, 25 DEG C of viscosity are 6500mPas,
Step (2) takes above-mentioned polyether glycol 60g, polyester polyol 40g, foam stabilizer (AK-8805) 3g, amines catalyst (N according to mass parts, N-dimethylcyclohexylamine) 0.76g, metal-based catalysts isocaprylic acid potassium 0.75g, Potassium ethanoate 0.5g, water 1.5g, pentamethylene 15g mixing and stirring be mixed with combined polyether, then in cup, add aforesaid combination polyethers 11.6g, polymethine polyphenyl polyisocyanate 20.1g successively, mechanical stirring 10s under rotating speed 3000-3500r/min condition, obtained urethane foam oxygen index is 32.3%.
4. prepare the method for high flame retardant hard polyurethane foams as claimed in claim 3 for one kind, it is characterized in that: on four-necked bottle, load onto reflux condensing tube, 302g cardanol is added in four-necked bottle, paraformaldehyde 72g, bromamide 66g stirred under nitrogen atmosphere mixes, be warming up to 80 DEG C, drip diethanolamine 200g, time for adding is 1h, then at 90 DEG C, 4h is reacted, continue to be warming up to 110 DEG C, decompression dehydration makes moisture be less than 1.0%, pass into 80g oxyethane and 162g propylene oxide reaction continuously, temperature controls at about 130 DEG C, still internal pressure remains on 0.4 1 0.6MPa, when pressure cooling is for normal pressure, polyreaction terminates, at 110 DEG C of insulation 2h, vacuumize 30min, obtain modification cardanol Mannich polyether glycol, its hydroxyl value is 402mg/gKOH, 25 DEG C of viscosity are 6500mPas, then above-mentioned polyether glycol 60g, polyester polyol 40g, foam stabilizer (AK-8805) 3g, amines catalyst (N is taken according to mass parts, N-dimethylcyclohexylamine) 0.76g, metal-based catalysts isocaprylic acid potassium 0.75g, Potassium ethanoate 0.5g, water 1.5g, pentamethylene 15g mixing and stirring be mixed with combined polyether, then in cup, add aforesaid combination polyethers 11.6g, polymethine polyphenyl polyisocyanate 20.1g successively, mechanical stirring 10s under rotating speed 3000-3500r/min condition, obtained urethane foam oxygen index is 32.3%.
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