CN104231304B - The liquifying method of discarded polyisocyanurate foamed plastics and its liquefaction polyalcohol of preparation - Google Patents
The liquifying method of discarded polyisocyanurate foamed plastics and its liquefaction polyalcohol of preparation Download PDFInfo
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- CN104231304B CN104231304B CN201410543773.4A CN201410543773A CN104231304B CN 104231304 B CN104231304 B CN 104231304B CN 201410543773 A CN201410543773 A CN 201410543773A CN 104231304 B CN104231304 B CN 104231304B
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- Prior art keywords
- foamed plastics
- catalyst
- liquefaction
- polyalcohol
- polyisocyanurate
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- 239000011495 polyisocyanurate Substances 0.000 title claims abstract description 41
- 229920003023 plastic Polymers 0.000 title claims abstract description 40
- 239000004033 plastic Substances 0.000 title claims abstract description 40
- 229920000582 polyisocyanurate Polymers 0.000 title claims abstract description 40
- 150000005846 sugar alcohols Polymers 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000012634 fragment Substances 0.000 claims abstract description 23
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 238000006136 alcoholysis reaction Methods 0.000 claims abstract description 14
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 8
- 229940043276 diisopropanolamine Drugs 0.000 claims description 8
- 229910052681 coesite Inorganic materials 0.000 claims description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 229910052682 stishovite Inorganic materials 0.000 claims description 7
- 229910052905 tridymite Inorganic materials 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 4
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 4
- 229940043237 diethanolamine Drugs 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 4
- 229940102253 isopropanolamine Drugs 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical class CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 claims description 2
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 claims description 2
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical class CCC(O)CO BMRWNKZVCUKKSR-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
- 229960005082 etohexadiol Drugs 0.000 claims description 2
- MHIBEGOZTWERHF-UHFFFAOYSA-N heptane-1,1-diol Chemical compound CCCCCCC(O)O MHIBEGOZTWERHF-UHFFFAOYSA-N 0.000 claims description 2
- 229940051250 hexylene glycol Drugs 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229960004418 trolamine Drugs 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 229910052593 corundum Inorganic materials 0.000 claims 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 1
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 1
- 239000006260 foam Substances 0.000 abstract description 20
- 239000000463 material Substances 0.000 abstract description 13
- 229920005830 Polyurethane Foam Polymers 0.000 abstract description 9
- 239000011496 polyurethane foam Substances 0.000 abstract description 9
- 229920005862 polyol Polymers 0.000 abstract description 2
- 150000003077 polyols Chemical class 0.000 abstract description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 29
- 238000009413 insulation Methods 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
- 238000010792 warming Methods 0.000 description 14
- 229910020628 SiW12O40 Inorganic materials 0.000 description 7
- 239000004814 polyurethane Substances 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 229920002635 polyurethane Polymers 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 150000002513 isocyanates Chemical class 0.000 description 5
- 238000005829 trimerization reaction Methods 0.000 description 5
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000004088 foaming agent Substances 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 229920001228 polyisocyanate Polymers 0.000 description 3
- 239000005056 polyisocyanate Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- -1 tetramethyl diaminourea Chemical compound 0.000 description 3
- QVTVDJWJGGEOGX-UHFFFAOYSA-N urea;cyanide Chemical compound N#[C-].NC(N)=O QVTVDJWJGGEOGX-UHFFFAOYSA-N 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OYWRDHBGMCXGFY-UHFFFAOYSA-N 1,2,3-triazinane Chemical compound C1CNNNC1 OYWRDHBGMCXGFY-UHFFFAOYSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 description 1
- GNDMWRNTJIARLO-UHFFFAOYSA-N ClC(C)Cl.[F] Chemical class ClC(C)Cl.[F] GNDMWRNTJIARLO-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- XEUCQOBUZPQUMQ-UHFFFAOYSA-N Glycolone Chemical compound COC1=C(CC=C(C)C)C(=O)NC2=C1C=CC=C2OC XEUCQOBUZPQUMQ-UHFFFAOYSA-N 0.000 description 1
- UWIULCYKVGIOPW-UHFFFAOYSA-N Glycolone Natural products CCOC1=C(CC=CC)C(=O)N(C)c2c(O)cccc12 UWIULCYKVGIOPW-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- XADCESSVHJOZHK-UHFFFAOYSA-N Meperidine Chemical compound C=1C=CC=CC=1C1(C(=O)OCC)CCN(C)CC1 XADCESSVHJOZHK-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000008365 aqueous carrier Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000004651 carbonic acid esters Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical class CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229940035423 ethyl ether Drugs 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- UKACHOXRXFQJFN-UHFFFAOYSA-N heptafluoropropane Chemical compound FC(F)C(F)(F)C(F)(F)F UKACHOXRXFQJFN-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000003471 mutagenic agent Substances 0.000 description 1
- 231100000707 mutagenic chemical Toxicity 0.000 description 1
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention relates to a kind of liquifying method of discarded polyisocyanurate foamed plastics, comprise the following steps：（1）Discarded polyisocyanurate foamed plastics are crushed, polyisocyanurate foamed plastics fragment is obtained；（2）Polyisocyanurate foamed plastics fragment, alcoholysis agent and catalyst are added into reactor, nitrogen is passed through and is reacted；（3）After reaction terminates, alcamine compound is added, nitrogen is passed through and continues to react, reacted rear Filtration of catalyst, obtained the polyalcohol that liquefies.The invention further relates to the liquefaction polyalcohol prepared by it.The present invention is using environment-friendly supported heteropolyacid class catalyst as catalyst, and polyisocyanurate foam liquefaction efficiency is up to more than 95%；Free from admixture is remained in liquefaction polyalcohol, and material system is homogeneous；The polyurethane foam plastics obtained using liquefaction polyols preparation, product shows preferable mouldability, and property indices can reach the standards of GB/T 26,689 2011.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of liquid of discarded polyisocyanurate foamed plastics
Change method and its liquefaction polyalcohol of preparation.
Background technology
Polyisocyanurate foamed plastics are the important high polymer materials of a class, by polyethers or polyester and excessive poly- isocyanide
Urea acid esters is prepared under catalyst action, due to containing substantial amounts of isocyanate trimerization heterocycle in material so that poly- isocyanide
Urea acid esters foamed plastics is more stablized, with excellent heat resistance, cold resistance and anti-flammability, the container that is widely used, building
The fields such as exterior wall, pipe insulation.
Service life is reached using the product of polyisocyanurate foam, substantial amounts of poly-isocyanurate can be produced after scrapping
Foam waste, the method that landfill is usually taken and burns is handled, and causes land wastage and the pollution of air.Under the pressure of environment pressure
Power, the whole world such as Bayer, BASF, Air Products and Chemicals, Tao Shi esbablished corporation has been carried out on polyurethane foam
The recovery technology research of foam.It is that waste polyurethane foam is recycled to study at present more, and common technology includes Physical and change
Method.
The method that physiochemical mutagens are utilized is not to destroy polyurethane general chemical structure as means, such as patent CN
101096426A, CN101560309A, CN101987484, CN1560104A, CN101838454, CN 1651511A etc. is reported
Method, be first to crush solid polyurethane waste material, be further used as filling polyurethane material and use, have bonding extrusion forming, be extruded into
Type, injection moulding, hot-forming etc., material common mechanical poor-performing prepared by physical recovering method method, it is impossible to play polyurethane
The high advantage of the strength of materials.
Polyurethane chemistry recycle frequently with method：Reacted after polyurethane material is crushed with alcohol in catalyst action
Under be degraded into liquid.Used as patent CN1180689A, USP3404103, CN102516593A, US6759260B2 are disclosed
Oxide or hydroxide or the Lewis acid of alkali metal carry out foam degraded as catalyst；USP3708440 is disclosed in tool
In the presence of having the aliphatic dihydroxy alcohol of 2-6 carbon atom and two alkanolamines with 4-8 carbon atom, by about 175
DEG C to polyurethane foam is heated at 250 DEG C, the foam is transformed into polyalcohol；CN 102504331A, which are disclosed, uses poly- carbonic acid
Ester dihydric alcohol as alcoholysis agent, the number-average molecular weight of the PCDL is 500-20000, the polyalcohol of gained
Hydroxyl value≤90mgKOH/g.The object of above method research is mainly isocyanate trimerization ring in polyurethane foam, polyurethane foam
Content is relatively low, and degraded is mainly the urea bond disconnected with alcohol in foam, amino-formate bond, and three a small amount of polycyclics can be partly dissolved
In degradation solution, and contain substantial amounts of isocyanate trimerization ring in polyisocyanurate material, because trimerization ring structure is very firm,
Using above method open loop DeGrain, suspended wherein containing certain solid flocculent substance in material after degradation reaction, this
A little suspensions are that some do not have liquefied well-set foams,, due to material heterogeneity, belong to a kind of solidliquid mixture, make
Obtaining the material can not continue to be used in foamed material.
The content of the invention
The invention reside in solving, isocyanate trimerization ring structure in discarded polyisocyanurate foamed plastics is stable caused
The low deficiency of open loop efficiency is there is provided a kind of liquifying method of discarded polyisocyanurate foamed plastics, and it comprises the following steps:
（1）Discarded polyisocyanurate foamed plastics are crushed, polyisocyanurate foamed plastics fragment is obtained；
（2）Polyisocyanurate foamed plastics fragment, alcoholysis agent and catalyst are added into reactor, nitrogen progress is passed through
Reaction；
（3）After reaction terminates, alcamine compound is added, nitrogen is passed through and continues to react, catalysis is filtered to remove after having reacted
Agent, obtains the polyalcohol that liquefies；
The alcoholysis agent is dihydric alcohol and/or trihydroxylic alcohol, and the catalyst is supported heteropolyacid class catalyst.
The present invention uses dihydric alcohol and/or trihydroxylic alcohol as alcoholysis agent, because dihydric alcohol trihydroxylic alcohol steric hindrance is smaller,
Hydroxyl is more active, is easier to participate in the reaction with amino-formate bond.
Step（2）Described in polyisocyanurate foamed plastics fragment using being added portionwise, it is 1~6 time to add number of times, excellent
Elect as 3~5 times.The catalyst can be recycled and reused, and the number of times recycled and reused is 3-10 times, preferably 4-6 times.
Step（2）In reaction temperature be 100 DEG C -210 DEG C, preferably 130-190 DEG C；Reaction time is 1-15 hours,
Preferably 3-10 hours.Step（2）It is middle easily to be reached using the benefit temperature of these reaction conditions, and energy consumption is relatively low
Step（3）In reaction temperature be 120 DEG C -200 DEG C, preferably 130-180 DEG C；Reaction pressure is 0.1-
1.5MPa, preferably 0.2-1.0 MPa；Reaction time is 1-10 hours, preferably 3-9 hours.Step（3）It is middle to be reacted using these
The benefit of condition is the high activity radical reaction produced in amino and chain breaking process so that material system more stable homogeneous.
Step（2）The weight ratio of middle polyisocyanurate foamed plastics fragment, alcoholysis agent and catalyst is 100：（30-
250）：（0.5-10）, the weight ratio of preferred polyisocyanurate foamed plastics fragment, alcoholysis agent and catalyst is 100：（30-
200）：（0.5-3）.The benefit that weight ratio between fragment, alcoholysis agent and catalyst three is selected in the range of this is alcoholysis agent
Consumption is low, and degradation effect is preferable.
Step（3）The alcamine compound and step of middle addition（2）The weight ratio of the alcoholysis agent of middle addition is 0.2-30：
100 so that degraded is more abundant.
The alcamine compound is selected from monoethanolamine, diethanol amine, triethanolamine, isopropanolamine, diisopropanolamine (DIPA), three
The mixture of one or more kinds of arbitrary proportions in isopropanolamine, methylethanolamine, N, N- dimethylisopro panolamines.
The dihydric alcohol is selected from ethylene glycol, propane diols, 1,2- butanediols, BDO, 1,2- pentanediols, 1,5- penta 2
Alcohol, hexylene glycol, heptandiol, ethohexadiol, diethylene glycol, triethylene glycol, polyethylene glycol, DPG, tripropylene glycol, polypropylene glycol
One or both of any of the above ratio mixture；The trihydroxylic alcohol be glycerine, trimethylolpropane in one kind or
Two kinds of arbitrary proportion mixing.
The molecular formula of the supported heteropolyacid class catalyst is HnAB12O40/ Z, wherein n are 3-6, and A is hetero atom, A choosings
From the mixing of one or both of hetero atom P, Si arbitrary proportion；B is coordination atom, and B is selected from one or both of Mo, W and appointed
Meaning ratio is mixed；Z is carrier, and Z is selected from carrier active carbon, SiO2、Al2O3, it is a kind of in macropore MCM-41 molecules；The solid-carrying type is miscellaneous
The mass ratio of heteropoly acid and carrier is 10~50% in many acid catalysts.Supported heteropolyacid class catalysis of the present invention
Agent is prepared using existing preparation method, specific as follows：The heteropoly acid aqueous solution and carrier are tuned into thick slurry in proportion, turned
Enter the reactor with stirring, in 90~120 DEG C of 15~20h of stirring reaction, then vacuum filtration removing moisture, is dried, after roasting
Produce.
The invention further relates to the liquefaction polyalcohol obtained by the above method, the hydroxyl value of the liquefaction polyalcohol is 310-
780mgKOH/g, acid number are 0.1-1.5mgKOH/g, viscosity 1200-50000mPas（@25℃）, moisture≤0.15%.
The preparation-obtained liquefaction polyalcohol of the present invention can prepare polyurethane foam plastics as raw material, using existing
The method for preparing polyurethane foam plastics, it is specific as follows：By liquefaction polyalcohol, polyalcohol, water, catalyst, foam stabiliser and
Combined polyether is first made after foaming agent mixing, then combined polyether reacts with polyisocyanates, can prepare of good performance poly-
Urethane foamed plastics.Above-mentioned liquefaction polyalcohol, polyalcohol, water, catalyst, the weight ratio of foam stabiliser and foaming agent are（10-
80）：（20-70）：（0-2）：（0.2-3.0）：（0.5-4.0）：（8-30）；The hydroxyl value of polyalcohol is 120-650mgKOH/g, many
Isocyanate index is 2.0-3.0.
Above-mentioned catalyst can be using conventional catalyst in the art, preferably N, N- dimethyl cyclohexyl amines, Sanya second
Base diamines, N, N- dimethyl benzylamines, three（Dimethylamino-propyl）Hexahydrotriazine, pentamethyl-diethylenetriamine, tetramethyl diaminourea
In ethylether, lupetazin, N-methylmorpholine, N-ethylmorpholine, 1,2- methyl miaow, TMR-2, TMR-3, TMR-4, DMP-30
One or two kinds of arbitrary proportions mixing.
Above-mentioned foaming agent can be using conventional foaming agent in the art, preferably pentamethylene, pentane, isopentane, fourth
Two or more mixture in alkane, a fluorine dichloroethanes, pentafluoropropane, 3-pentafluorobutane, heptafluoro-propane.
Above-mentioned foam stabiliser is using conventional foam stabiliser in the art, it would however also be possible to employ the German Gao Shi meter Te trades mark
For B8460, B8461, B8462, B8465, B8471, B8474, B8476, B8481 product；GE companies of the U.S. trade mark is
L6900, L6988, L6912 product；The dolantin Shi Chuan companies trade mark is AK8805, AK8815, AK8812, AK8809 product,
Dow Corning Corporation foam stabiliser DC5604, DC5357, foam stabiliser can be it is one of above-mentioned or above-mentioned in two
Plant or two or more arbitrary proportions are used in mixed way.
Above-mentioned polyisocyanates be polymethine polyphenyl polyisocyanate, the preferably Desmodur N of Bayer companies,
44V20L, 44V10L etc.；The Superace5005 of Huntsman companies, 2085 etc.；The PAPI127 of DOW companies；BASF AG
The MR200 in three well East Asia, the C1130 of Japanese NPU companies, the PM2010 of domestic Yantai Wanhua company.
Compared to the prior art the present invention, has the following advantages that：
1st, catalyst, polyisocyanurate foam liquefaction effect are used as using environment-friendly supported heteropolyacid class catalyst
Really good, free from admixture is remained in liquefaction polyalcohol, and material system is homogeneous, and polyisocyanurate foam liquefaction efficiency is up to more than 95%；
2nd, after catalyst filtration, it can be used for multiple times；
3rd, the polyurethane foam plastics obtained using liquefaction polyols preparation, product shows preferable mouldability, every
Performance indications can reach GB/T 26689-2011 standards.
Embodiment
The present invention is described in further details below by example：
Polyisocyanurate foamed plastics powder is fragmentated first.
Embodiment 1
By 180 grams of ethylene glycol, H4SiW12O40/SiO2（H4SiW12O40With SiO2Mass ratio be 36%）3.3 grams, poly- isocyanide
100 grams of urea acid esters chipped foam adds the 2L stainless steel reactors with condensation reflux unit, and stirring is warming up to 150 DEG C, then will
200 grams of polyisocyanurate foamed plastics fragments are added in reactor in two times（One time 120 grams, one time 80 grams）, it is passed through nitrogen
Gas, normal pressure, insulation reaction 5h；30 grams of diethanol amine is added, stirring is warming up to 160 DEG C, and inflated with nitrogen make it that the pressure of reactor is
0.5MPa, insulation reaction 5h, filters out catalyst, obtains the polyalcohol 1 that liquefies.
The above-mentioned product index of liquefaction polyalcohol 1：Hydroxyl value 560mgKOH/g, acid number are 1.4mgKOH/g, viscosity
12500mPa·s（@25℃）, moisture 0.11%.
Embodiment 2
By 200 grams of glycerine, H3PW12O40/SiO2（H3PW12O40With SiO2Mass ratio be 30%）4.5 grams, poly- isocyanide urea
120 grams of acid esters chipped foam adds the 2L stainless steel reactors with condensation reflux unit, and stirring is warming up to 170 DEG C, then by 230
Gram polyisocyanurate foamed plastics fragment is added in reactor in two times（One time 120 grams, one time 110 grams）, nitrogen is passed through,
Normal pressure, insulation reaction 5h；30 grams of triethanolamine, 5 grams of monoethanolamine, 10 grams of triisopropanolamine are added, stirring is warming up to 170 DEG C,
Inflated with nitrogen make it that the pressure of reactor is 0.8MPa, insulation reaction 6h, filters out catalyst, obtains the polyalcohol 2 that liquefies.
The above-mentioned product index of liquefaction polyalcohol 2：Hydroxyl value 436mgKOH/g, acid number are 1.0mgKOH/g, viscosity 8500mPa
s（@25℃）, moisture 0.10%.
Embodiment 3
By 120 grams of DPG, 40 grams of trimethylolpropane, H4SiMo12O40/C （H4SiMo12O40With the matter of activated carbon
Amount is than being 39%）5.0 grams, the 110 grams of 2L stainless steel reactions of addition with condensation reflux unit of polyisocyanurate foam fragment
Device, stirring is warming up to 150 DEG C, then 210 grams of polyisocyanurate foamed plastics fragments are added in reactor in three times（Every time
70 grams）, it is passed through nitrogen, normal pressure, insulation reaction 5h；15 grams of diisopropanolamine (DIPA) is added, stirring is warming up to 160 DEG C, and inflated with nitrogen causes
The pressure of reactor is 0.8MPa, insulation reaction 7h, filters out catalyst, obtains the polyalcohol 3 that liquefies.
The above-mentioned product index of liquefaction polyalcohol 3：Hydroxyl value 650mgKOH/g, acid number are 1.5mgKOH/g, viscosity
35500mPa·s（@25℃）, moisture 0.15%.
Embodiment 4
The H that 170 grams of propane diols, 30 grams of diethylene glycol, 10 grams of glycerine, embodiment 1 are reclaimed4SiW12O40/ SiO2
3.3 grams, the 100 grams of 2L stainless steel reactors of addition with condensation reflux unit of polyisocyanurate foamed plastics fragment, stirring
150 DEG C are warming up to, then 200 grams of polyisocyanurate foamed plastics fragments are added in reactor in two times（One time 110 grams,
One time 90 grams）, it is passed through nitrogen, normal pressure, insulation reaction 4h；28 grams of triisopropanolamine is added, stirring is warming up to 150 DEG C, inflated with nitrogen
So that the pressure of reactor is 0.9MPa, insulation reaction 8h, catalyst is filtered out, the polyalcohol 4 that liquefies is obtained.
The above-mentioned product index of liquefaction polyalcohol 4：Hydroxyl value 690mgKOH/g, acid number are 1.3mgKOH/g, viscosity
59500mPa·s（@25℃）, moisture 0.12%.
Embodiment 5
By 230 grams of BDO, H4SiW12O40/Al2O3 （H4SiW12O40With Al2O3 Mass ratio be 31%）5.0 grams,
90 grams of polyisocyanurate foamed plastics fragment adds the 2L stainless steel reactors with condensation reflux unit, and stirring is warming up to
100 DEG C, then 210 grams of polyisocyanurate foamed plastics fragments are added in reactor in two times（One time 110 grams, one time 100
Gram）, it is passed through nitrogen, normal pressure, insulation reaction 7h；8 grams of triisopropanolamine, 2 grams of isopropanolamine are added, stirring is warming up to 130 DEG C, filled
Nitrogen make it that the pressure of reactor is 0.7MPa, insulation reaction 5h, filters out catalyst, obtains the polyalcohol 5 that liquefies.
The above-mentioned product index of liquefaction polyalcohol 5：Hydroxyl value 463mgKOH/g, acid number are 1.0mgKOH/g, viscosity
26500mPa·s（@25℃）, moisture 0.11%.
Embodiment 6
By 230 grams of BDO, 70 grams of 1,2- pentanediols, H4SiW12O40/Al2O3 （H4SiW12O40With Al2O3 Matter
Amount is than being 31%）24 grams, the 90 grams of 2L stainless steel reactions of addition with condensation reflux unit of polyisocyanurate foamed plastics fragment
Device, stirring is warming up to 200 DEG C, and by polyisocyanurate foamed plastics fragment, 210 grams are added in reactor in two times（Once
110 grams, one time 100 grams）, it is passed through nitrogen, normal pressure, insulation reaction 10h；50 grams of triisopropanolamine, 10 grams of diethanol amine are added, is stirred
Mix and be warming up to 180 DEG C, inflated with nitrogen make it that the pressure of reactor is 1.2MPa, insulation reaction 8h, filters out catalyst, is liquefied
Polyalcohol 6.
The above-mentioned product index of liquefaction polyalcohol 6：Hydroxyl value 718mgKOH/g, acid number are 0.85mgKOH/g, viscosity
9800mPa·s（@25℃）, moisture 0.12%.
Embodiment 7
By 120 grams of DPG, 40 grams of trimethylolpropane, 434 grams of DPG, H4SiMo12O40/C
（H4SiMo12O40Mass ratio with activated carbon is 39%）23 grams, 110 grams of polyisocyanurate foam fragment added with condensing back
The 2L stainless steel reactors of device are flowed, stirring is warming up to 190 DEG C, then divides three by 210 grams of polyisocyanurate foamed plastics fragments
It is secondary to be added in reactor（70 grams every time）, it is passed through nitrogen, normal pressure, insulation reaction 5h；Add 60 grams of diisopropanolamine (DIPA), N, N- bis-
23 grams of methyl isopropyl hydramine, stirring is warming up to 180 DEG C, and inflated with nitrogen causes the pressure of reactor to be 1.3MPa, insulation reaction 9h, mistake
Catalyst is filtered out, the polyalcohol 7 that liquefies is obtained.
The above-mentioned product index of liquefaction polyalcohol 7：The mgKOH/g of hydroxyl value 688, acid number are 0.99mgKOH/g, viscosity 8850
mPa·s（@25℃）, the % of moisture 0.1.
The performance data for the liquefaction polyalcohol that various embodiments of the present invention are prepared is as shown in table 1.
The liquefaction polyalcohol that the present invention is prepared is formulated as described in table 2 and prepares polyisocyanurate foamed plastics.
Note：PPG 1：Hydroxyl value 330mgKOH/g, viscosity 16000mPas（@25℃）, moisture 0.10%；Polyethers is more
First alcohol 2：Hydroxyl value 480mgKOH/g, acid number 1.1mgKOH/g, viscosity 4500mPas（@25℃）, moisture 0.15%.
From Table 2, it can be seen that using the liquefaction polyalcohol for preparing of the present invention as raw material prepare it is poly- different
Cyanurate foamed plastics, product shows preferable mouldability, and property indices can be up to GB/T 26689-2011 marks
It is accurate.Described above is only inventive embodiments, not makees any formal limitation to the present invention, any to be familiar with this skill
The personnel of art can be changed or be modified to the equivalent embodiment of equivalent variations using above-mentioned technology contents, every without departing from this hair
The content of bright technical scheme, belongs to technical solution of the present invention scope.
Claims (6)
1. a kind of liquifying method of discarded polyisocyanurate foamed plastics, it is characterised in that comprise the following steps：
(1) discarded polyisocyanurate foamed plastics are crushed, obtains polyisocyanurate foamed plastics fragment；
(2) toward addition polyisocyanurate foamed plastics fragment, alcoholysis agent and catalyst in reactor, it is passed through nitrogen and carries out instead
Should；
(3) after reaction terminates, alcamine compound is added, nitrogen is passed through and continues to react, reacted rear Filtration of catalyst, obtained
To liquefaction polyalcohol；
The alcoholysis agent is dihydric alcohol and/or trihydroxylic alcohol, and the catalyst is supported heteropolyacid class catalyst；
The weight ratio of polyisocyanurate foamed plastics fragment, alcoholysis agent and catalyst is 100 in step (2)：(30-250)：
(0.5-10)；
The alcamine compound is selected from monoethanolamine, diethanol amine, triethanolamine, isopropanolamine, diisopropanolamine (DIPA), three isopropyls
The mixture of one or more kinds of arbitrary proportions in hydramine, methylethanolamine, N, N- dimethylisopro panolamines；
The molecular formula of the supported heteropolyacid class catalyst is HnAB12O40/ Z, wherein n are 3-6, the one kind of A in P, Si
Or both arbitrary proportion mixing；B is selected from the mixing of one or both of Mo, W arbitrary proportion；Z is selected from carrier active carbon, SiO2、
Al2O3It is a kind of in macropore MCM-41 molecules.
2. liquifying method according to claim 1, it is characterised in that the reaction temperature in step (2) is 100 DEG C -210 DEG C,
Reaction time is 1-15 hours.
3. liquifying method according to claim 1, it is characterised in that the reaction temperature in step (3) is 120 DEG C -200 DEG C,
Reaction pressure is 0.1-1.5MPa, and the reaction time is 1-10 hours.
4. liquifying method according to claim 1, it is characterised in that the alcamine compound and step added in step (3)
(2) the weight ratio of the alcoholysis agent added in is 0.2-30：100.
5. the liquifying method according to any one of claims 1 to 3, it is characterised in that the dihydric alcohol is selected from ethylene glycol, third
Glycol, 1,2- butanediols, BDO, 1,2- pentanediols, 1,5-PD, hexylene glycol, heptandiol, ethohexadiol, diethyl two
One or both of alcohol, triethylene glycol, polyethylene glycol, DPG, tripropylene glycol, polypropylene glycol any of the above ratio it is mixed
Compound；The trihydroxylic alcohol is the mixing of one or both of glycerine, trimethylolpropane arbitrary proportion.
6. a kind of liquefaction polyalcohol obtained by claim 1 to 5 any one methods described, it is characterised in that the liquefaction is more
The hydroxyl value of first alcohol be 310-780mgKOH/g, acid number be 0.1-1.5mgKOH/g, 25 DEG C when viscosity be 1200-50000mPas,
Moisture≤0.15%.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3983087A (en) * | 1974-04-29 | 1976-09-28 | The Upjohn Company | Novel process of reclaiming polyurethane foam |
| CA2216772A1 (en) * | 1996-10-18 | 1998-04-18 | Bernhard Naber | Production of polyisocyanurate foams having a reduced thermal conductivity |
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2014
- 2014-10-15 CN CN201410543773.4A patent/CN104231304B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3983087A (en) * | 1974-04-29 | 1976-09-28 | The Upjohn Company | Novel process of reclaiming polyurethane foam |
| CA2216772A1 (en) * | 1996-10-18 | 1998-04-18 | Bernhard Naber | Production of polyisocyanurate foams having a reduced thermal conductivity |
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