CN1621429A - Combined polyol for polyisocyanurate foam - Google Patents
Combined polyol for polyisocyanurate foam Download PDFInfo
- Publication number
- CN1621429A CN1621429A CN200410067142.6A CN200410067142A CN1621429A CN 1621429 A CN1621429 A CN 1621429A CN 200410067142 A CN200410067142 A CN 200410067142A CN 1621429 A CN1621429 A CN 1621429A
- Authority
- CN
- China
- Prior art keywords
- polyol
- polyisocyanurate foam
- foam according
- combined
- combined polyol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000006260 foam Substances 0.000 title claims abstract description 31
- 229920005862 polyol Polymers 0.000 title claims abstract description 22
- 150000003077 polyols Chemical class 0.000 title claims abstract description 22
- 239000011495 polyisocyanurate Substances 0.000 title claims abstract description 19
- 229920000582 polyisocyanurate Polymers 0.000 title claims abstract description 14
- -1 polyethylene Polymers 0.000 claims abstract description 21
- 239000003063 flame retardant Substances 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 11
- 229920000570 polyether Polymers 0.000 claims abstract description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 10
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 10
- 229920000768 polyamine Polymers 0.000 claims abstract description 9
- 239000000654 additive Substances 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract 3
- 150000001412 amines Chemical class 0.000 claims abstract 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 9
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000012948 isocyanate Substances 0.000 claims description 7
- 150000002513 isocyanates Chemical class 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 4
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 claims description 3
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 150000008065 acid anhydrides Chemical class 0.000 claims description 3
- 238000012644 addition polymerization Methods 0.000 claims description 3
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical group OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 3
- 150000002894 organic compounds Chemical class 0.000 claims description 3
- 229940059574 pentaerithrityl Drugs 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- MHZDONKZSXBOGL-UHFFFAOYSA-N propyl dihydrogen phosphate Chemical compound CCCOP(O)(O)=O MHZDONKZSXBOGL-UHFFFAOYSA-N 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229960004418 trolamine Drugs 0.000 claims description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 claims description 2
- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- 239000004902 Softening Agent Substances 0.000 claims description 2
- YYQRGCZGSFRBAM-UHFFFAOYSA-N Triclofos Chemical compound OP(O)(=O)OCC(Cl)(Cl)Cl YYQRGCZGSFRBAM-UHFFFAOYSA-N 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000007514 bases Chemical class 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 230000001408 fungistatic effect Effects 0.000 claims description 2
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 claims description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 claims description 2
- 239000010458 rotten stone Substances 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 229960001147 triclofos Drugs 0.000 claims description 2
- 230000002087 whitening effect Effects 0.000 claims description 2
- 230000003712 anti-aging effect Effects 0.000 claims 1
- 239000004205 dimethyl polysiloxane Substances 0.000 claims 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims 1
- 150000002191 fatty alcohols Chemical class 0.000 claims 1
- 239000003112 inhibitor Substances 0.000 claims 1
- 239000012188 paraffin wax Substances 0.000 claims 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims 1
- 238000009413 insulation Methods 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 5
- 239000000779 smoke Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 2
- 239000011810 insulating material Substances 0.000 abstract description 2
- 239000004698 Polyethylene Substances 0.000 abstract 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 abstract 1
- 238000005260 corrosion Methods 0.000 abstract 1
- 230000007797 corrosion Effects 0.000 abstract 1
- 150000004985 diamines Chemical class 0.000 abstract 1
- 238000002955 isolation Methods 0.000 abstract 1
- 229920000573 polyethylene Polymers 0.000 abstract 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 9
- 239000011496 polyurethane foam Substances 0.000 description 9
- 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 description 7
- 238000005187 foaming Methods 0.000 description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 5
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 3
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 description 2
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical group CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 description 1
- NFVPEIKDMMISQO-UHFFFAOYSA-N 4-[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC=C(O)C=C1 NFVPEIKDMMISQO-UHFFFAOYSA-N 0.000 description 1
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 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 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- CIXSDMKDSYXUMJ-UHFFFAOYSA-N n,n-diethylcyclohexanamine Chemical compound CCN(CC)C1CCCCC1 CIXSDMKDSYXUMJ-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 150000004885 piperazines Chemical class 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 229960004249 sodium acetate Drugs 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Abstract
The polyol composition for polyisocyanurate foam consists of: polyester polyols based on aromatic acid anhydride 40-70 wt%; polyethylene/propylene oxide polyether polyols based on fatty amine, fatty diamine or fatty polyamine 0-10 wt%; compound containing active hydrogen atom 0-25 wt%, liquid organic fire retardant 14-25 wt%, water 1-3 wt%, catalyst 2-4.5 wt%, and supplementary material and/or additives 2-5 wt%. The hard foam prepared through one-step process has homogeneous and fine cells, and has the excellent performances in electric insulation, light weight, sound isolation, chemical corrosion resistance, etc. similar to those of PUR foam as well as pressure strength, size stability, heat insulation, flame resistance, low burning smoke amount, etc. superior to PUR foam. The present invention may be used in heat insulating material and sandwiched composite material with relatively high temperature requirement.
Description
Technical field
What the present invention relates to is a kind of polyvalent alcohol that is used for the foam materials field, particularly a kind of combined polyol for polyisocyanurate foam.
Background technology
Since generating this method of hard polyurethane foams by organic isocyanate and combination polyol reaction in the presence of the whipping agent and being established, hard polyurethane foams (PUR) is little because of its thermal conductivity, specific tenacity is high, the characteristics of in light weight, resistance to chemical attack, has been subjected in material fields such as building, insulation, transportation, insulation more and more using and paying close attention to.But, common PUR rigid foam if for a long time under high temperature or severe cold environment yielding and ultimate compression strength can descend, range of application is restricted.And as a kind of organic polymer material, the PUR rigid foam is the same with other organism to exist incendive objective fact in flame.To relating to the flame retardant resistance of materials such as building, industry, transportation, domestic life in different use occasions, country has proposed strict standard and has implemented criterion.
" urethane foam " second edition Fang Yusheng, Zhu Lvmin etc. write, and the 458th page, have described the fire retardant research application that is applicable to hard polyurethane foams at present and mainly have been summarised as: additive flame retardant and reactive flame retardant.This two based flame retardant plays inhibition foamy combustionvelocity because of containing flame retardant resistance element phosphor and/or halogen.But the foam that contains above-mentioned two based flame retardants exists significant disadvantages, because the phosphorous or halogen element compound of volatility escapes in the fireworks, smog is rolled up and with poisonous irritant gas when promptly in a single day foam burns.Smog has reduced visibility, and delay the crowd escape the inferno, toxic gas can stimulate the people respiratory system, make the people poison, lose consciousness, and this causes personnel death's major cause just in fire failure.Improve the stability of PUR rigid foam and the problem that the flame retardant resistance technology has become scientific research personnel's growing interest.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, provide a kind of poly-isocyanurate (PIR) porous plastics with making up polyvalent alcohol.Make the low-smoke of its rigid foam that makes when possessing conventional P UR foam premium properties and have simultaneously better dimensional stability, thermotolerance, flame resistant penetrance and foam burning again concurrently.
The present invention is achieved by the following technical solutions, and weight percentages of components of the present invention is: based on the polyester polyol 40～70% of aromatic anhydride, based on aliphatic series single-, two-or the polyethylene oxide/propylene oxide polyether glycol 0～10% of polyamines, the compound 0～25% that contains reactive hydrogen atom, liquid organic fire-retardant 14～25%, moisture 1～3%, catalyzer 2～4.5%, subsidiary material and/or additive: 2～5%.
Described polyester polyol based on aromatic anhydride is to form with aromatic anhydride and polyvalent alcohol polycondensation, and aromatic anhydride comprises: Tetra hydro Phthalic anhydride, phthalic acid, m-phthalic acid or its acid anhydride, preferred Tetra hydro Phthalic anhydride.
Described polyester polyol molecular-weight average is 200～700, and functionality is 2-8.The polyvalent alcohol that is suitable for has: ethylene glycol (EG), propylene glycol (PG), glycol ether (DEG), butyleneglycol, glycerol, hexanetriol, TriMethylolPropane(TMP), tetramethylolmethane, sorbyl alcohol etc.With the alcohols that has three-functionality-degree is good, can play the intensity and the flame resistant effect that improve rigid foam.Can use less or, reduce production costs in the combination polyvalent alcohol without fire retardant.
Described single based on aliphatic series, two-or polyamines polyether glycol, be with aliphatic series single-, two-or polyamines be initiator, by with oxyalkylene hydro carbons such as oxyethane, propylene oxide, oxybutylene, oxidation dodecylene or Styrene oxide 98min., preferred propylene oxide or oxyethane, addition polymerization makes polyether glycol.
Described polyether glycol molecular-weight average is 100～300, wherein aliphatic single, two-or polyamines mainly comprise: quadrol, diethylenetriamine, thanomin, diethanolamine, trolamine, N-methyl-or N-ethyldiethanolamine, 1,3-propylene diamine, 1,3-or 1,4-butanediamine or 1,2-, 1,3-, 1,4-, 1,5-or 1, the oligopolymer of 6-hexamethylene-diamine, quadrol, the oligopolymer of quadrol comprises: diethylenetriamine, Triethylenetetramine (TETA) or penten.
Described polyether glycol preferably is that initiator and weight percent are 70～100 1,2 epoxy prapane and 0～30 oxyethane mixture addition polymerization with the quadrol.
Hydrogen atom, molecular-weight average that the described compound that contains reactive hydrogen atom refers to contain at least 2 energy and isocyanate-reactive are 60～500, the polyvalent alcohol of functionality in 3～8 scopes.Mainly comprise ethylene glycol, glycol ether, propylene glycol, glycerine, tetramethylolmethane or polyhydroxy-alcohols such as sucrose, sorbyl alcohol.
Described liquid organic fire-retardant is the organic compound that trichlorine propyl phosphate, trichloroethyl phosphate contain haloid element or phosphoric.Comprise: inferior adjacent triphenyl phosphate ester (TPP), tricresyl phosphate (1-chloro-2-sec.-propyl) ester (TCPP), triethyl phosphate (TEP).Preferred TCPP, TEP.
The described liquid organic compound that contains haloid element or phosphoric, the PIR foaming system can reach high flame resistance and low-smoke, if but can add that some are phosphorous/or halogen element, gained foamy flame retardant resistance will be better, and the amount of being fuming during burning can not rise.
Described moisture further limits its weight percent and is: 0.5～2.0%.
Described catalyzer can promote urethane and the reaction of poly-isocyanuric acid simultaneously.What be suitable for has: aminated compounds, contain the isoionic organic alkali metal salt of potassium sodium, metal organic monoacid salt, quaternary ammonium salt compound, organic basic compound.Wherein with: 2,4,6-three (dimethylamino methyl) phenol, 2-(N, the N dimethylamine ylmethyl) phenol, N, N-diethyl cyclohexylamine N, N ', N " symmetrical six piperazines of-three (dimethyl amido propyl group), N; N-dimethyl ethylenimine, N, N-dimethylethanolamine, N-methylmorpholine, N-ethylmorpholine, two (dimethyl aminoethyl) ether, trolamine, N methyldiethanol amine, Potassium ethanoate, sodium-acetate etc. are preferred.Above catalyzer can singlely use, and also can mix use, improves catalytic effect.Serve as preferred with aminated compounds and metal organic monoacid saline admixture among the present invention.
Described optional subsidiary material and/or additive refer to suds-stabilizing agent or use pigment, tinting material, antiager, softening agent or have mildew-resistant and the material of fungistatic effect, perhaps use filler, as barium sulfate, tripoli, carbon black or whitening agent.Wherein suds-stabilizing agent is the known polysiloxane compounds of some technician.
The present invention need not to change the rigid foam somatocyte fine and even that adopts the single stage method foaming to make under production unit and the process condition, has the characteristics that make its low-smoke when multiple premium propertiess such as having the insulation of conventional P UR foam, lightweight, sound insulation, resistance to chemical attack concurrently also has than the better ultimate compression strength of PUR foams, dimensional stability and thermal insulation, flame resistant penetrability and burning simultaneously in the time of these two kinds of segmented structure of carbamate and isocyanuric acid ester.Therefore PIR system porous plastics can satisfy heat-insulating material or the sandwich composite board material that temperature is had higher service requirements.System of the present invention is applicable to the adiabatic heat-insulation or the lagging material of oil tank, transition pipeline pipeline outside.
Embodiment
Provide four specific embodiments in conjunction with content of the present invention, but the present invention is not only for therewith.All marks by weight among the embodiment.
The raw material that relates among the embodiment has:
1. combination polyol blends:
The molecular weight that forms with o-2 potassium acid acid anhydride and polyvalent alcohol polycondensation is 300 polyester polyol; It with the molecular weight of quadrol initiator poly(propylene oxide)/epoxidized polyether polyvalent alcohol of 200; The compound that contains reactive hydrogen atom: glycerine; Fire retardant: trichlorine propyl phosphate (TCPP); Catalyzer: containing metal potassium or sodium ion organic monoacid salt/pair (dimethyl aminoethyl) ether=(0～0.3)/(1～4); Water; Subsidiary material and/or additive: suds-stabilizing agent.
2. with the component of the supporting reaction of aforesaid combination polyol blends: organic multiple isocyanate and whipping agent.
Organic multiple isocyanate is rough diphenylmethanediisocyanate (thick MDI).This thick MDI composition comprises 2,4 '-diphenylmethanediisocyanate (2,4 '-MDI), 4,4 '-diphenylmethanediisocyanate (4,4 '-MDI), with 2, three kinds of isomer mixtures of 2 '-MDI.The trade mark that the organic multiple isocyanate composition that uses among the present invention is produced as Bayer company is the thick MDI of 44V20L, and its NCO content is: 31.5%.
Isocyanic ester and polyvalent alcohol two composition weight are approaching in different and traditional (PUR) foaming system, and (PIR) isocyanic ester is a main raw material in the foaming system, and organic multiple isocyanate parts by weight/polyol blends parts by weight should be less than 1.7 among the present invention.
Mainly comprise as indispensable whipping agent in combination polyvalent alcohol and the different hydrogen acid ether foaming process: water, fluoro trichloromethane (F-11), dichlorotrifluoroethane (HCFC-123) or trifluorotrichloroethane lower boiling halohydrocarbon such as (HCFC-141b).A preferred trifluorotrichloroethane (HCFC-141b) cooperates combination polyol blends of the present invention and the foaming of above-mentioned organic multiple isocyanate, can obtain the foam of low heat conductivity.Foaming agents content is counted 25～45 parts for good with 100 parts of weight of combination polyol blends.
| Combination polyvalent alcohol weight percent | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Polyester polyol based on aromatic anhydride | 70 | ?55 | ?50 | ?40 |
| Aliphatic series is single-, two-or polyamines polyether glycol | 10 | ?5 | ?0 | ?0 |
| The compound that contains reactive hydrogen atom | 0 | ?12.5 | ?20 | ?25 |
| Liquid organic fire-retardant | 14 | ?20 | ?19.5 | ?25 |
| Moisture | 1.0 | ?1.4 | ?2.0 | ?3 |
| Catalyzer | 3.0 | ?2.6 | ?4.5 | ?2.0 |
| Subsidiary material and/or additive | 2.0 | ?3.5 | ?4.0 | ?5.0 |
With combination polyvalent alcohol supporting reactive component:
| Whipping agent: (HCFC-141b) | ????30 | ????36 | ????27 | ????25 |
| Organic multiple isocyanate: 44V20L | ????190 | ????184 | ????170 | ????175 |
The beneficial effect that above-mentioned three embodiment can obtain and the contrast table of regular convention formula effect:
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Regular convention formula | ||
| Nuclear core density | (Kg/m 3) | 38.7 | ?38.1 | ?38.7 | ?38.5 | ?36.5 |
| Thermal conductivity | (mW/mK) | 19.8 | ?20.3 | ?21.2 | ?21.3 | ?21.8 |
| During ultimate compression strength 10% stress (Mpa) | Parallel and ascent direction | 0.24 | ?0.24 | ?0.18 | ?0.18 | ?0.19 |
| Vertical and ascent direction | 0.23 | ?0.21 | ?0.16 | ?0.16 | ?0.15 | |
| Dimensional stability volume change (%) | 48hrs，-30℃ | -0.28 | ?-0.20 | ?-0.25 | ?-0.26 | ?-0.80 |
| 48hrs，100℃ | +0.79 | ?+0.65 | ?+0.70 | ?+0.72 | ?3.17 | |
| Rate of closed hole | (％) | 97.34 | ?98.62 | ?96.47 | ?96.53 | ?95.43 |
| Water-intake rate | (100cm 2/g) | 1.90 | ?1.87 | ?2.62 | ?2.63 | ?2.82 |
| Oxygen index | (％) | 28.0 | ?27.4 | ?27.0 | ?26.9 | ?＜26 |
Claims (10)
1, a kind of combined polyol for polyisocyanurate foam, it is characterized in that weight percentages of components is: based on the polyester polyol 40～70% of aromatic anhydride, single based on aliphatic series, two-or the polyethylene oxide/propylene oxide polyether glycol 0～10% of polyamines, the compound 0～25% that contains reactive hydrogen atom, liquid organic fire-retardant 14～25%, moisture 1～3%, catalyzer 2～4.5%, subsidiary material and/or additive: 2～5%.
2, combined polyol for polyisocyanurate foam according to claim 1, it is characterized in that, described polyester polyol based on aromatic anhydride is with Tetra hydro Phthalic anhydride, phthalic acid, m-phthalic acid or its acid anhydride, the polyester polyol that forms with polyol condensating.
3, combined polyol for polyisocyanurate foam according to claim 2 is characterized in that, described polyester polyol molecular-weight average is 200～700, and functionality is 2-8; Described polyvalent alcohol is: ethylene glycol, propylene glycol, glycol ether, butyleneglycol, glycerol, hexanetriol, TriMethylolPropane(TMP), tetramethylolmethane, sorbyl alcohol.
4, combined polyol for polyisocyanurate foam according to claim 1, it is characterized in that, described polyether glycol be single with aliphatic series, two-or polyamines be initiator by being with weight percent: 70～100 1,2 epoxy prapane and weight percent are: it is 100～300 polyether glycol that 0～30 oxyethane mixture addition polymerization makes molecular-weight average.
5, combined polyol for polyisocyanurate foam according to claim 4, it is characterized in that, described aliphatic series is single, two-or polyamines comprise: quadrol, diethylenetriamine, thanomin, diethanolamine, trolamine, N-methyl-or N-ethyldiethanolamine, 1,3-propylene diamine, 1,3-or 1,4-butanediamine or 1,2-, 1,3-, 1,4-, 1,5-or 1, the oligopolymer of 6-hexamethylene-diamine, quadrol.
6, combined polyol for polyisocyanurate foam according to claim 1, it is characterized in that the described compound that contains reactive hydrogen atom should contain the hydrogen atom of 2 energy and isocyanate reaction at least, molecular weight is 60～500, the polyvalent alcohol of functionality in 3～8 scopes.
7, combined polyol for polyisocyanurate foam according to claim 1 is characterized in that, described liquid organic fire-retardant is the organic compound that trichlorine propyl phosphate, trichloroethyl phosphate contain haloid element or phosphoric.
8, combined polyol for polyisocyanurate foam according to claim 1 is characterized in that, described moisture further limits its weight percent and is: 0.5～2.0%.
9, combined polyol for polyisocyanurate foam according to claim 1, it is characterized in that, described catalyzer is the mixture of amines catalyst and metal organic monoacid saline catalyst, comprising: aminated compounds, contain the isoionic organic alkali metal salt of potassium sodium, metal organic monoacid salt, quaternary ammonium salt compound, organic basic compound.
10, combined polyol for polyisocyanurate foam according to claim 1, it is characterized in that, described subsidiary material and/or additive are meant suds-stabilizing agent, use paraffin or Fatty Alcohol(C12-C14 and C12-C18) or dimethyl polysiloxane, oxidation inhibitor or anti-aging agent, pigment or tinting material, softening agent and have mildew-resistant and the material of fungistatic effect, perhaps use filler, as barium sulfate, tripoli, carbon black or whitening agent.
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| CNB2004100671426A CN100523040C (en) | 2004-10-14 | 2004-10-14 | Combined polyol for polyisocyanurate foam |
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| CNB2004100671426A CN100523040C (en) | 2004-10-14 | 2004-10-14 | Combined polyol for polyisocyanurate foam |
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| CN100523040C CN100523040C (en) | 2009-08-05 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102276778A (en) * | 2011-06-15 | 2011-12-14 | 上海大唐盛隆制冷科技有限公司 | Fire-retardant polyurethane hard foam material and preparation method thereof |
| CN105246934A (en) * | 2013-06-07 | 2016-01-13 | 科思创德国股份公司 | Elastic rigid foam having improved temperature stability |
| CN106167541A (en) * | 2016-08-01 | 2016-11-30 | 山东诺威新材料有限公司 | Continuous way produces PIR bulk bubble combined polyether and its preparation method and application |
| CN106750211A (en) * | 2016-12-16 | 2017-05-31 | 上海华峰材料科技研究院（有限合伙） | Good aromatic polyester polyol and preparation method thereof with pentamethylene compatibility |
| CN107299692A (en) * | 2017-08-28 | 2017-10-27 | 天津市奇才防水材料有限公司 | A kind of water-proof heat-preserving integrated plate |
| CN111253548A (en) * | 2020-01-22 | 2020-06-09 | 黎明化工研究设计院有限责任公司 | Sound-absorbing polyurethane hard foam composite material for vehicle |
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2004
- 2004-10-14 CN CNB2004100671426A patent/CN100523040C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102276778A (en) * | 2011-06-15 | 2011-12-14 | 上海大唐盛隆制冷科技有限公司 | Fire-retardant polyurethane hard foam material and preparation method thereof |
| CN105246934A (en) * | 2013-06-07 | 2016-01-13 | 科思创德国股份公司 | Elastic rigid foam having improved temperature stability |
| CN106167541A (en) * | 2016-08-01 | 2016-11-30 | 山东诺威新材料有限公司 | Continuous way produces PIR bulk bubble combined polyether and its preparation method and application |
| CN106167541B (en) * | 2016-08-01 | 2019-03-15 | 山东一诺威新材料有限公司 | Continous way produces PIR bulk bubble combined polyether and its preparation method and application |
| CN106750211A (en) * | 2016-12-16 | 2017-05-31 | 上海华峰材料科技研究院（有限合伙） | Good aromatic polyester polyol and preparation method thereof with pentamethylene compatibility |
| CN107299692A (en) * | 2017-08-28 | 2017-10-27 | 天津市奇才防水材料有限公司 | A kind of water-proof heat-preserving integrated plate |
| CN111253548A (en) * | 2020-01-22 | 2020-06-09 | 黎明化工研究设计院有限责任公司 | Sound-absorbing polyurethane hard foam composite material for vehicle |
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| CN100523040C (en) | 2009-08-05 |
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