JPS6131726B2 - - Google Patents
Info
- Publication number
- JPS6131726B2 JPS6131726B2 JP53124342A JP12434278A JPS6131726B2 JP S6131726 B2 JPS6131726 B2 JP S6131726B2 JP 53124342 A JP53124342 A JP 53124342A JP 12434278 A JP12434278 A JP 12434278A JP S6131726 B2 JPS6131726 B2 JP S6131726B2
- Authority
- JP
- Japan
- Prior art keywords
- foam
- urethane
- equivalent
- producing
- organic polyisocyanate
- 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.)
- Expired
Links
- 239000006260 foam Substances 0.000 claims description 60
- 229920001228 polyisocyanate Polymers 0.000 claims description 25
- 239000005056 polyisocyanate Substances 0.000 claims description 25
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 19
- -1 polyphenylene Polymers 0.000 claims description 19
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 19
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 17
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 239000004593 Epoxy Substances 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 7
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 7
- 229920000570 polyether Polymers 0.000 claims description 7
- 229920000265 Polyparaphenylene Polymers 0.000 claims description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 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 claims description 5
- 239000004604 Blowing Agent Substances 0.000 claims description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 5
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical group [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 239000000203 mixture Substances 0.000 description 11
- 229920005862 polyol Polymers 0.000 description 10
- 150000003077 polyols Chemical class 0.000 description 10
- 230000009257 reactivity Effects 0.000 description 9
- 239000003063 flame retardant Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 150000001734 carboxylic acid salts Chemical class 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000005829 trimerization reaction Methods 0.000 description 3
- 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 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000010097 foam moulding Methods 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- 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 1
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 description 1
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- GXBYFVGCMPJVJX-UHFFFAOYSA-N Epoxybutene Chemical compound C=CC1CO1 GXBYFVGCMPJVJX-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- 150000008043 acidic salts Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000004872 foam stabilizing agent Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002483 hydrogen compounds Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000642 polymer Polymers 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
- 239000011591 potassium Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
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ãè¡šãDETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a urethane-modified rigid isocyanurate foam, and more specifically, a urethane-modified rigid isocyanurate foam having a homogeneous fine cell structure with low brittleness and excellent heat resistance and flame retardance. Relating to a manufacturing method. It is already known to trimerize polyisocyanates in the presence of catalysts to produce rigid isocyanurate foams containing isocyanurate rings. Since this hard foam has isocyanurate rings, it is generally superior to urethane foam in terms of heat resistance and flame retardancy. On the other hand, conventional hard isocyanurate foams are not only highly brittle but also difficult to control reactions during manufacturing.
Since the foam-forming reaction occurs non-uniformly, it does not have a homogeneous fine cell structure and is hardly of practical use. In order to improve the above-mentioned drawbacks, when trimerizing polyisocyanate, by coexisting a polyol containing hydroxyl groups less than the equivalent of the isocyanate group, urethane bonds are introduced into the polymer chain, and urethane-modified hard isocyanate It has been proposed to produce nurate foams. but,
Even with this manufacturing method, the brittleness of the hard foam obtained is not sufficiently improved, and furthermore, it is difficult to control the reactivity during manufacturing, and in particular, the hardening of the foam surface is difficult compared to the hardening of the inside of the foam. Because of the slow curing, a foam with a homogeneous and fine cell structure could not be obtained. Attempts have been made to improve these drawbacks by using a large amount of polyol, but this results in a problem of reduced heat resistance and flame retardancy. The present invention was made to solve the above-mentioned problems, and has low brittleness, heat resistance,
A urethane-modified hard isocyanate that can obtain a hard foam with a homogeneous fine cell structure with excellent flame retardancy, and also allows the reactivity of the curing reaction to be adjusted depending on the use of the hard foam. An object of the present invention is to provide a method for manufacturing Nurate foam. The present invention provides at least one organic polyisocyanate selected from the group consisting of polyphenylene polymethylene polyisocyanate and diphenylmethane diisocyanate, at least one glycol selected from the group consisting of ethylene glycol and diethylene glycol, and trimethylol. A polyether triol with a hydroxyl value of 200 to 1000 mgKOH/g obtained by adding ethylene oxide to propane is used, and the hydroxyl equivalent of the glycol and the hydroxyl equivalent of the polyether triol are each 0.05 to 1,000 to 1 equivalent of the isocyanate group of the organic polyisocyanate. 0.8, and the reaction is carried out in the presence of a catalyst consisting of triethylenediamine and an epoxy compound, a blowing agent, and a foam stabilizer such that the total value of both does not exceed 1. The organic polyisocyanate used in the present invention is polyphenylene polymethylene polyisocyanate, diphenylmethane diisocyanate, and mixtures thereof, preferably polyphenylene polymethylene polyisocyanate. Here, polyphenylene polymethylene polyisocyanate is also called crude MDI (C-MDI), and is a mixture of polynuclear polyisocyanates represented by the following formula, and the average value of n is usually:
It is 0.1-1.3. In addition, prepolymers obtained by reacting these organic polyisocyanates described above with various active hydrogen compounds, preferably polyols described below, in a state with an excess of isocyanate groups, partial allophanatization, trimerization, etc. of these organic polyisocyanates, Carbodiimidized modified isocyanates are also preferably used. Isocyanates other than the organic polyisocyanates specified above are not suitable for producing rigid foams with excellent physical properties according to the present invention. The polyol used in the present invention has a hydroxyl value of 200 to 1000 mgKO obtained by adding ethylene oxide to at least one glycol selected from the group consisting of ethylene glycol and diethylene glycol, and trimethylolpropane.
H/g, particularly preferably 300 to 500 mgKOH/g, and these polyols contain 0.05 to 0.8 equivalents, preferably 0.1 to 0.5 equivalents of the above glycol per equivalent of isocyanate group. , the above polyether triol is
0.05 to 0.8 equivalents, preferably 0.1 to 0.5 equivalents, and the amount does not exceed 1 equivalent in total, preferably 0.1 to 0.5 equivalents.
0.85 equivalents are used, particularly preferably 0.2 to 0.7 equivalents. Alkylene glycols, polyalkylene glycols such as propylene glycol, dipropylene glycol, polypropylene glycol, etc.
Polyester polyols have poor reactivity, require a large amount of catalyst when reacting with organic polyisocyanates, and do not form a rigid foam having a homogeneous and fine cell structure. In addition, the hydroxyl value
A polyether polyol of 200 mgKOH/g or less also requires a large amount of polyether polyol or catalyst to obtain the reactivity necessary for foam formation, which reduces the heat resistance and flame retardance of the resulting hard foam. Not suitable for use in In the present invention, the blending ratio of the above-specified polyol to the organic polyisocyanate is appropriately selected within the above-mentioned range depending on the use of the rigid foam. On the other hand, the use of diethylene glycol speeds up the foam-forming reaction, so by appropriately combining the two, it is useful to adjust the reactivity of the reaction system over a wide range according to the purpose without impairing the physical properties of the foam. Ethylene oxide adducts to trimethylolpropane also help improve the hardenability of the foam surface. Generally, in the formation reaction of a cured isocyanurate foam, the reaction on the surface is slower than that inside the foam, and if a gradual reaction is attempted to form the foam, the surface of the foam will be insufficiently hardened and the surface will not be homogeneous. I can't get the form. Also, the resulting foam is brittle. On the other hand, if a foam is formed by rapid reaction, it becomes difficult to inject the resin liquid into the mold and the foaming pressure increases, making it difficult to apply to cast molding. According to the present invention, the hardenability of the foam surface can be improved by adding an ethylene oxide adduct to trimethylolpropane, and at the same time, the reactivity of the reaction system can be adjusted by using ethylene glycol and diethylene glycol. Accordingly, a homogeneous rigid foam can be manufactured while ensuring appropriate reactivity. Next, the trimerization catalyst used in the present invention is a catalyst consisting of a combination of an epoxy compound and triethylenediamine. The epoxy compound used is not particularly limited. Specific examples include glycidyl ethers of alcohols such as n-butyl glycidyl ether, allyl glycidyl ether, and glycerin triglycidyl ether; glycidyl ethers of phenols such as phenyl glycidyl ether, resolming glycidyl ether, and diglycidyl ether of bisphenol A; Examples include glycidyl ether of carboxylic acids such as glycidyl methacrylate, vinylcyclohexene diepoxide, butadiene epoxide, epoxidized soybean oil, styrene oxide, etc., but particularly preferred are phenyl glycidyl ether and/or dicrycidyl of bisphenol A. It is ether. In such a catalyst, the epoxy compound is preferably used in an amount of 0.005 to 0.1 equivalent per equivalent of isocyanate group,
Further, triethylenediamine is used in an amount of 0.01 to 2 parts by weight per 100 parts by weight of the organic polyisocyanate. This epoxy compound-triethylenediamine catalyst imparts relatively mild reactivity to the reaction system. If necessary, an alkali metal salt and/or alkaline earth metal salt of carboxylic acid is used in combination with the epoxy compound-triethylenediamine catalyst. Examples of carboxylic acids include acetic acid, propionic acid,
Examples include, but are not limited to, aliphatic mono- and dicarboxylic acids such as 2-ethylhexanoic acid and adipic acid, and aromatic mono- and dicarboxylic acids such as benzoic acid and phthalic acid. Preferable examples of the alkali metals to form the carboxylic acid salt include sodium and potassium, and preferable examples of the alkaline earth metal include calcium, but of course the metals are not limited to these. but,
In the present invention, the carboxylic acid salt particularly preferably used is potassium acetate. The carboxylate catalyst as described above has, per equivalent of isocyanate group,
Preferably, 0.03 equivalent or less is used. In addition, in the case of dicarboxylic acid, it may be either a neutral salt or an acidic salt. When used in combination with an epoxy compound-triethylenediamine catalyst, the carboxylate catalyst has the effect of accelerating the curing of the reaction system, improving the curing of the foam surface, and further reducing the amount of triethylenediamine used. Further, if desired, in the present invention, a known trimerization catalyst or urethanization catalyst may be used in combination with the above catalyst. Foaming agents and foam stabilizers that have been commonly used in the past can be used as appropriate, and are not particularly limited. As the blowing agent, for example, inert low-boiling halogenated hydrocarbons such as trichlorofluoromethane, trichlorotrifluoroethane, and methylene chloride are used. Water is also used. Examples of the foam stabilizer include various silicone surfactants used in the production of urethane foam. Additives such as flame retardants and fillers are also used as necessary. As the flame retardant, phosphorus-based flame retardants, halogen-based flame retardants, and other known flame retardants are usually used to make urethane foam flame retardant. Examples of the filler include synthetic resin powder, glass powder, silica, alumina, aluminum hydroxide, calcium carbonate, ammonium phosphate, antimony oxide powder, foamed glass particles, foamed perlite, etc.
Various materials such as inorganic granular foams such as expanded vermiculite and shirasu balloons, and fibrous materials such as glass fibers, carbon fibers, synthetic fibers, and cellulose fibers can be used as appropriate depending on the purpose of the rigid foam. In producing the urethane-modified rigid isocyanurate foam according to the present invention, each component is mixed by conventionally known methods and equipment,
Although it can be formed into a foam, it is convenient to prepare a mixture of mutually inert components in advance and use a double mixture when forming the foam. For example, a mixture consisting of an organic polyisocyanate, an epoxy compound and a portion of the required amount of a blowing agent, and triethylenediamine, a carboxylic acid salt,
A mixture consisting of the polyol, the remainder of the blowing agent, and the foam stabilizer is prepared separately, and these two mixtures are mixed during foam molding. Preparing mixtures of each component individually in this manner is advantageous in that the individual mixtures usually have a storage stability of two weeks or more. The present invention will be explained in more detail with reference to Examples below. The method of the present invention allows the reaction in foam molding to be controlled by reacting a specific organic polyisocyanate and a specific polyol in the presence of a specific catalyst. At the same time, it has improved the hardenability of the foam surface, making it possible to produce a urethane-modified rigid isocyanurate foam that is less brittle and has a homogeneous fine cell structure with a high closed cell ratio. Furthermore, the rigid foam obtained by the method of the present invention retains the excellent heat resistance and flame retardancy possessed by isocyanurate foam. Examples Polyphenylene polymethylene polyisocyanate (trade name "Takenate RL-15P", Takeda Pharmaceutical Company Limited) and diglycidyl ether of bisphenol A (trade name "Prominate YD-128", Takeda Pharmaceutical Company Limited) ) at a weight ratio of 100:5 (hereinafter referred to as P solution) was prepared.
Separately, prepare a mixed solution (hereinafter referred to as R
It's called liquid. ) was prepared. This P liquid and R liquid are combined with Freon in the amounts shown in the table below.
After stirring and mixing for 10 seconds, the mixture was immediately poured into a 25 cm cubic cake box and allowed to freely foam at room temperature to produce a urethane-modified rigid isocyanurate foam. The equivalent ratio of isocyanate groups to hydroxyl values in this case is also shown in the table. The physical properties of the hard foam obtained as described above are summarized in a table. As is clear from comparison with the hard foam obtained in the comparative example described below, the hard foam obtained by the present invention has a particularly large impact value,
In addition to significantly improved brittleness, the surface hardening properties were excellent, and the cell state was homogeneous and fine. Furthermore, it is clear from a comparison of Examples 2 and 3 with Example 1 that the carboxylic acid salt as a catalyst increases the reactivity. Incidentally, the impact value was measured using a DuPont impact tester. A cylindrical striking core with a diameter of 2.5 cm is placed on a foam sample with a thickness of 5 cm, and 500 g is placed on top of the foam sample from a height of 50 cm.
The depth of the hole formed in the foam sample (1 cm) was measured by dropping a weight, and the impact value was determined using the following formula. Impact value = 55.2/l (lbã»in/in) Comparative example In exactly the same manner as in the example, R liquid having the composition shown in the table was stirred and mixed with Freon together with P liquid, and then
Immediate free expansion was carried out to produce a rigid foam.
The physical properties are shown in the table. ãtableã
Claims (1)
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ãããªãŒã ã®è£œé æ¹æ³ã[Scope of Claims] 1. At least one organic polyisocyanate selected from the group consisting of polyphenylene polymethylene polyisocyanate and diphenylmethane diisocyanate, and at least one glycol selected from the group consisting of ethylene glycol and diethylene glycol. , a polyether triol with a hydroxyl value of 200 to 1000 mgKOH/g obtained by adding ethylene oxide to trimethylolpropane, and the hydroxyl equivalent of the glycol and the hydroxyl equivalent of the polyether triol based on 1 equivalent of isocyanate group of the organic polyisocyanate. is 0.05 to 0.8, respectively, and the total of both does not exceed 1. The reaction is carried out in the presence of a catalyst containing triethylenediamine and an epoxy compound as main components, a blowing agent, and a foam stabilizer. A method for producing urethane-modified rigid isocyanurate foam. 2. A patent claim characterized in that 0.01 to 2 parts by weight of triethylene diamine is used with respect to 100 parts by weight of organic polyisocyanate, and 0.005 to 0.1 equivalent of an epoxy compound is used with respect to 1 equivalent of isocyanate group of the organic polyisocyanate. A method for producing a urethane-modified rigid isocyanurate foam according to Item 1. 3. The method for producing a urethane-modified rigid isocyanurate foam according to claim 1 or 2, wherein the epoxy compound is diglycidyl ether of bisphenol A. 4. The urethane-modified hard isocyanurate according to any one of claims 1 to 3, wherein the catalyst comprises triethylenediamine, an epoxy compound, and an alkali metal salt or alkaline earth metal salt of a carboxylic acid. Method of manufacturing foam. 5. The method for producing a urethane-modified rigid isocyanurate foam according to claim 4, characterized in that 0.03 equivalent or less of the carboxylic acid metal salt is used per equivalent of the isocyanate group of the organic polyisocyanate. 6. The method for producing a urethane-modified rigid isocyanurate foam according to any one of claims 4 to 6, wherein the carboxylic acid metal salt is potassium acetate.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP12434278A JPS5552313A (en) | 1978-10-09 | 1978-10-09 | Manufacture of urethane-modified rigid isocyanurate foam |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP12434278A JPS5552313A (en) | 1978-10-09 | 1978-10-09 | Manufacture of urethane-modified rigid isocyanurate foam |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5552313A JPS5552313A (en) | 1980-04-16 |
JPS6131726B2 true JPS6131726B2 (en) | 1986-07-22 |
Family
ID=14882975
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP12434278A Granted JPS5552313A (en) | 1978-10-09 | 1978-10-09 | Manufacture of urethane-modified rigid isocyanurate foam |
Country Status (1)
Country | Link |
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JP (1) | JPS5552313A (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5565214A (en) * | 1978-11-10 | 1980-05-16 | Bridgestone Corp | Preparation of flame-resistant polyisocyanurate foam |
JPS6215216Y2 (en) * | 1980-05-30 | 1987-04-17 | ||
KR20180059491A (en) * | 2015-09-23 | 2018-06-04 | ë°ì€í ìì€ìŽ | Rigid polyurethane foam with improved insulation and mechanical properties |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS50114393A (en) * | 1974-01-30 | 1975-09-08 | ||
JPS52103495A (en) * | 1976-02-24 | 1977-08-30 | Bayer Ag | Process for producing thermally moldable polyisocyanurate foam |
-
1978
- 1978-10-09 JP JP12434278A patent/JPS5552313A/en active Granted
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS50114393A (en) * | 1974-01-30 | 1975-09-08 | ||
JPS52103495A (en) * | 1976-02-24 | 1977-08-30 | Bayer Ag | Process for producing thermally moldable polyisocyanurate foam |
Also Published As
Publication number | Publication date |
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JPS5552313A (en) | 1980-04-16 |
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