CN114075318A - Method for stably storing isocyanurate composition - Google Patents
Method for stably storing isocyanurate composition Download PDFInfo
- Publication number
- CN114075318A CN114075318A CN202010834506.8A CN202010834506A CN114075318A CN 114075318 A CN114075318 A CN 114075318A CN 202010834506 A CN202010834506 A CN 202010834506A CN 114075318 A CN114075318 A CN 114075318A
- Authority
- CN
- China
- Prior art keywords
- free radical
- isocyanate
- polyurethane
- isocyanate composition
- radical initiator
- 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.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 24
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 title description 8
- 239000012948 isocyanate Substances 0.000 claims abstract description 69
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 66
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 16
- 150000003254 radicals Chemical class 0.000 claims description 63
- -1 aromatic isocyanates Chemical class 0.000 claims description 41
- 239000003999 initiator Substances 0.000 claims description 41
- 150000003077 polyols Chemical class 0.000 claims description 36
- 229920005862 polyol Polymers 0.000 claims description 33
- 239000005056 polyisocyanate Substances 0.000 claims description 28
- 229920001228 polyisocyanate Polymers 0.000 claims description 28
- 229920002635 polyurethane Polymers 0.000 claims description 26
- 239000004814 polyurethane Substances 0.000 claims description 26
- 239000003112 inhibitor Substances 0.000 claims description 24
- 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 20
- 150000001412 amines Chemical class 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 150000002989 phenols Chemical group 0.000 claims description 14
- 238000005829 trimerization reaction Methods 0.000 claims description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
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- 150000003464 sulfur compounds Chemical class 0.000 claims description 8
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 6
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- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 3
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- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 3
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 3
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- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 230000002401 inhibitory effect Effects 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- XURVRZSODRHRNK-UHFFFAOYSA-N o-quinodimethane Chemical compound C=C1C=CC=CC1=C XURVRZSODRHRNK-UHFFFAOYSA-N 0.000 claims description 3
- NRNFFDZCBYOZJY-UHFFFAOYSA-N p-quinodimethane Chemical compound C=C1C=CC(=C)C=C1 NRNFFDZCBYOZJY-UHFFFAOYSA-N 0.000 claims description 3
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 9
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- 230000000052 comparative effect Effects 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 6
- 229920005906 polyester polyol Polymers 0.000 description 6
- 238000010526 radical polymerization reaction Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000000977 initiatory effect Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
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- 239000004033 plastic Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
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- 239000004417 polycarbonate Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 3
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
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- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000006082 mold release agent Substances 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 3
- 238000007348 radical reaction Methods 0.000 description 3
- 239000004250 tert-Butylhydroquinone Substances 0.000 description 3
- 235000019281 tert-butylhydroquinone Nutrition 0.000 description 3
- 229940043375 1,5-pentanediol Drugs 0.000 description 2
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 2
- 235000017491 Bambusa tulda Nutrition 0.000 description 2
- 241001330002 Bambuseae Species 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
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- 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 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000011425 bamboo Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
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- XXKOQQBKBHUATC-UHFFFAOYSA-N cyclohexylmethylcyclohexane Chemical compound C1CCCCC1CC1CCCCC1 XXKOQQBKBHUATC-UHFFFAOYSA-N 0.000 description 2
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- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
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- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 239000012934 organic peroxide initiator Substances 0.000 description 1
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- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 description 1
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- 235000021286 stilbenes Nutrition 0.000 description 1
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- 125000001424 substituent group Chemical group 0.000 description 1
- AUHHYELHRWCWEZ-UHFFFAOYSA-N tetrachlorophthalic anhydride Chemical compound ClC1=C(Cl)C(Cl)=C2C(=O)OC(=O)C2=C1Cl AUHHYELHRWCWEZ-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
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- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- SZHOJFHSIKHZHA-UHFFFAOYSA-N tridecanoic acid Chemical compound CCCCCCCCCCCCC(O)=O SZHOJFHSIKHZHA-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
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- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/089—Reaction retarding agents
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention relates to a method for stably storing an isocyanate composition, the stably stored isocyanate composition, and a polyurethane resin prepared from the isocyanate composition.
Description
Technical Field
The present invention relates to a method for the stable storage of isocyanate compositions, and to the stable storage of isocyanate compositions.
Background
The trimerization catalytic reaction of isocyanate is a curing and crosslinking method commonly used in the application field of polyurethane materials. The isocyanurate six-membered ring rigid structure generated by trimerization can provide high crosslinking degree to enhance the mechanical strength of the cured polyurethane material, and meanwhile, due to the high carbon-nitrogen-oxygen content of the isocyanurate six-membered ring and the excellent flame retardance generated by the conjugated aromatic structure, the integral flame retardance of the polyurethane material can be improved. For these reasons, the trimerization of isocyanate functions is widely used in the field of polyurethane materials. Generally, the trimerization reaction of isocyanates takes place in the presence of a trimerization catalyst. We have surprisingly found that in the presence of a free radical initiator, the isocyanate can trimerize even in the absence of a trimerization catalyst, i.e. an isocyanate composition to which a free radical initiator has been added will not be stable on storage because of the trimerization reaction. It is not known in the art how to make the trimerization of isocyanates with added free radical initiators slower or suppressed and to control the trimerization of isocyanates to occur either not or more controllably, so as to make the corresponding isocyanate compositions storage stable.
CN101675099A discloses a polymer composition containing a thermally activated free radical initiator comprising: (I) a free radical initiator, (II) a free radical crosslinkable polymer, (III) a scorch inhibiting and/or cure promoting amount of at least one of an isocyanate, a diisocyanate such as MDI, or a hydroxyalkyl (meth) acrylate compound such as hydroxyethyl (meth) acrylate, and optionally (IV) other scorch retarders and/or cure accelerators such as TEMPO compounds, hindered phenols, a-methylstyrene dimers, and the like. The free radical initiator may be any thermally activated compound that is relatively unstable and readily breaks into at least two free radicals, such as a peroxide or azo initiator. The crosslinkable polymer is a thermoplastic and/or elastomeric polymer that can be crosslinked (cured) by the action of a crosslinking agent, such as LDPE. The isocyanate, diisocyanate and (meth) acrylate scorch retardants and/or cure accelerators can be used alone or in combination with each other or optionally in combination with a TEMPO compound such as 4-hydroxy-TEMPO.
US5821296A discloses a polyurethane-polyester mixed resin system wherein the components of the system have improved shelf life stability. The resin system includes an a-side comprised of a multifunctional isocyanate and a free radical initiator. The hybrid resin system also includes a B-side comprising a hydroxyl terminated unsaturated polyester polyol, a vinyl unsaturated monomer, a polyurethane catalyst, a polymerization inhibitor, and optionally a peroxide accelerator, a chain extender, and a filler. The B-side polymerization inhibitor of the present invention includes a substituted hindered phenol type compound having a cyclic substituent which generates an activated benzylic hydrogen, a nitrophenol having a benzyl type substituent or not, naphthoquinone, a stable radical compound, and a mixture thereof.
CN101974307B discloses a polyurethane acrylate adhesive containing ionic groups and a preparation method thereof, wherein the adhesive comprises the following components in percentage by weight: 45-75 parts of macromolecular polyol, 1.5-3 parts of carboxylic acid compound or sulfonate, 15-30 parts of diisocyanate, 0.01-0.06 part of catalyst, 8-21 parts of monohydric alcohol containing acrylate groups and 0.01-0.06 part of free radical polymerization inhibitor, wherein the carboxylic acid compound or sulfonate is added into the macromolecular polyol, the diisocyanate and the catalyst are added after dehydration, the monohydric alcohol containing acrylate groups and the free radical polymerization inhibitor are added after temperature rise, a polyurethane acrylate polymer is obtained through temperature control reaction, and a mixture of a diluent and an initiator is added to obtain the product. Compared with the prior art, the invention contains ionic groups, so that the high-strength high-toughness high-molecular polyol has higher strength and toughness, and the multi-functionality high-molecular polyol also increases the mechanical strength of a system.
Despite the above disclosures, there remains a need in the art for a method of stably storing isocyanurate compositions.
Disclosure of Invention
In one aspect of the present invention, there is provided a method for stably storing an isocyanate composition comprising:
A1) one or more polyisocyanates;
A2) at least one free radical initiator;
which is the addition of component A3) at least one free-radical inhibitor to the isocyanate composition.
Preferably, the isocyanate composition is used for preparing a polyurethane resin.
Preferably, the polyisocyanate is selected from aromatic isocyanates, preferably diphenylmethane diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate or combinations thereof, particularly preferably diphenylmethane diisocyanate or (poly) diphenylmethane diisocyanate.
Preferably, the A2) free radical initiator is present in an amount of 0.1 to 5pbw, preferably 0.2 to 4pbw, more preferably 0.4 to 3pbw, based on 100pbw of the total weight of the isocyanate composition.
Preferably, the A2) free radical initiator is selected from peroxide and/or azo compounds.
Preferably, the peroxide is selected from the group consisting of ketone peroxides, peroxycarbonates, peroxyacyl, peroxyesters, hydrogen peroxide, alkyl peroxides, or any combination thereof.
Optionally, the azo compound is selected from azobisisobutyronitrile, azobisisoheptonitrile, or any combination thereof.
Preferably, the A3) free radical inhibitor is present in an amount of 0.001 to 2.0pbw, preferably 0.002 to 1pbw, more preferably 0.01 to 0.8pbw, based on the total weight of the isocyanate composition based on 100 pbw.
Preferably, said a3) radical inhibitor is selected from the group consisting of hindered and/or conjugated structure-containing phenols, amines and sulfur compounds, preferably hindered and/or conjugated structure-containing phenols, amines and sulfur compounds which react with primary or chain radicals to form non-radical species or stable radical species which can no longer initiate polymerization of the monomers, more preferably hindered phenols, hindered amines and phenothiazines, and especially hindered phenols.
Through repeated experiments, we have surprisingly found that isocyanates to which a radical initiator is added are susceptible to trimerization to form (poly) isocyanurates, so to speak, the radical initiator catalyzes the trimerization. Mixing the free-radical initiator directly in the isocyanate has an adverse effect on the transport and long-term storage of the isocyanate mixture. Particularly, under the condition of direct sunlight at high temperature in summer, the internal temperature of the common van-type transport vehicle can reach 50-60 ℃ in a sealed environment, so that the trimerization reaction of isocyanate can be promoted to occur in advance, and the quality of an isocyanate product is influenced. During some long haul shipping, ships may travel near the equator of the tropics for several weeks, and it is more difficult to ensure the quality of the isocyanate mixture to which the free radical initiator is added under such long term high temperature conditions. More surprisingly, we have found that the incorporation of a suitable amount of a free radical inhibitor in the isocyanate mixture effectively extends the storage time without any concern about quality problems even during transport under hot weather conditions. The method of the invention simply and effectively realizes the stable storage of the isocyanate composition, thereby simplifying the production process of the polyurethane resin, in particular to the polyurethane resin used for producing large products such as fan blades and the like, and improving the production efficiency.
In another aspect of the present invention, there is provided an isocyanate composition comprising the following components:
A1) one or more polyisocyanates;
A2) a free radical initiator; and
A3) at least one free radical inhibitor.
As described above, through a large number of experiments, we have unexpectedly found that the isocyanate composition of the present invention can be stably stored, and can be transported over long distances and stored for a long period of time even in hot weather.
In yet another aspect of the present invention, there is provided a process for preparing a (poly) isocyanurate by reacting an isocyanate composition comprising:
A1) one or more polyisocyanates;
A2) a free radical initiator; and
A3) at least one free radical inhibitor.
In a further aspect of the present invention there is provided the use of a free radical inhibitor for inhibiting the preparation of (poly) isocyanurates by the trimerisation of isocyanates catalysed by a free radical initiator.
Preferably, the free radical initiator is present in an amount of from 0.1 to 5pbw, preferably from 0.2 to 4pbw, more preferably from 0.4 to 3pbw, based on the total weight of the reaction system.
Preferably, the free radical inhibitor is present in an amount of 0.001 to 2.0pbw, preferably 0.002 to 1pbw, more preferably 0.01 to 0.8pbw, based on 100pbw of the total weight of the isocyanate composition.
In still another aspect of the present invention, there is provided a method for preparing a polyurethane resin by reacting a polyurethane reaction system comprising:
component A) comprising:
A1) one or more polyisocyanates;
A2) a free radical initiator;
A3) at least one free radical inhibitor;
component B) comprising:
B1) one or more organic polyols in an amount of 21 to 60 wt.%, based on the total weight of the polyurethane composition in 100 wt.%;
B2) one or more compounds having the structure of formula (I)
Wherein R1 is selected from hydrogen, methyl or ethyl; r2 is selected from alkylene having 2 to 6 carbon atoms, 2-bis (4-phenylene) -propane, 1, 4-bis (methylene) benzene, 1, 3-bis (methylene) benzene, 1, 2-bis (methylene) benzene; n is an integer selected from 1 to 6.
Preferably, wherein the B1) component is selected from one or more polyether polyols.
Preferably, wherein said B2) component is selected from: hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, or combinations thereof.
Preferably, the organic polyol is selected from the group consisting of polyols having a functionality of from 1.7 to 6, preferably from 1.9 to 4, more preferably from 1.9 to 2.8, and a hydroxyl number of 150 and 1100 mgKOH/g.
In still another aspect of the present invention, there is provided a polyurethane resin obtained by the method for preparing a polyurethane resin according to the present invention.
In a further aspect of the present invention, there is provided a polyurethane product comprising the aforementioned polyurethane resin of the present invention.
Preferably, the polyurethane product is selected from the group consisting of cable bridges, door and window curtain wall frames, ladder frames, tent poles or tubes, antiglare panels, floors, sucker rods, utility poles and crossarms, guardrails, grilles, architectural profiles, container profiles and sheets, bicycle frames, fishing poles, cable cores, insulator mandrels, radomes, single or sandwich continuous sheets, and leaf shells, webs, spar caps, joists, and blade roots of turbofan blades.
Drawings
The invention is illustrated below with reference to the accompanying drawings:
FIG. 1 shows infrared spectra of examples of the present invention and comparative examples. Wherein curve s1 in FIG. 1 represents the system spectrum for isocyanate 44V20 alone; the curve s2 in FIG. 1 shows that after 2pbw of TBPB had been added to the isocyanate 44V20, the viscosity had not changed during the initial phase; curve s3 in FIG. 1 shows the spectrum after 56 days of addition of 2pbw of TBPB to isocyanate 44V 20.
Detailed Description
The following terms used in the present invention have the following definitions or explanations.
pbw is the mass fraction of each component of the reaction system;
functionality, means according to the industry formula: functionality as measured by hydroxyl number molecular weight/56100; wherein the molecular weight is determined by GPC high performance liquid chromatography;
isocyanate index, which means a value calculated by the following formula:
any organic polyisocyanate may be used in the foregoing methods of the invention, including aromatic, aliphatic, and cycloaliphatic polyisocyanates and combinations thereof. The polyisocyanate can be represented by the general formula R (NCO) n, wherein R represents an aliphatic hydrocarbon group having 2 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 15 carbon atoms, an araliphatic hydrocarbon group having 8 to 15 carbon atoms, and n is 2 to 4.
Useful polyisocyanates include, but are not limited to, vinyl diisocyanate, tetramethylene 1, 4-diisocyanate, Hexamethylene Diisocyanate (HDI), dodecyl 1, 2-diisocyanate, cyclobutane 1, 3-diisocyanate, cyclohexane 1, 4-diisocyanate, 1-isocyanato 3, 3, 5-trimethyl 5-isocyanatomethylcyclohexane, hexahydrotoluene 2, 4-diisocyanate, hexahydrophenyl 1, 3-diisocyanate, hexahydrophenyl 1, 4-diisocyanate, perhydrodiphenylmethane 2, 4-diisocyanate, perhydrodiphenylmethane 4, 4-diisocyanate, phenylene 1, 3-diisocyanate, phenylene 1, 4-diisocyanate, stilbene 1, 4-diisocyanate, mixtures thereof, and mixtures thereof, 3, 3-dimethyl-4, 4-diphenyl diisocyanate, toluene-2, 4-diisocyanate (TDI), toluene-2, 6-diisocyanate
(TDI), diphenylmethane-2, 4 ' -diisocyanate (MDI), diphenylmethane-2, 2 ' -diisocyanate (MDI), diphenylmethane-4, 4 ' -diisocyanate (MDI), mixtures of diphenylmethane diisocyanates and/or homologues of diphenylmethane diisocyanates having more than one ring, polyphenylmethane polyisocyanates (polymeric MDI), naphthylene-1, 5-diisocyanates (NDI), their isomers, any mixtures between them and their isomers.
Useful polyisocyanates also include isocyanates obtained by modification with carbodiimide, allophanate, etc., preferably, but not limited to, diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, isomers thereof, mixtures thereof with isomers thereof.
When used in the present invention, the polyisocyanate includes an isocyanate dimer, trimer, tetramer or a combination thereof.
In certain embodiments of the present invention, the isocyanate is selected from an aromatic isocyanate, preferably diphenylmethane diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate or a combination thereof, particularly preferably diphenylmethane diisocyanate or (poly) diphenylmethane diisocyanate.
In a preferred embodiment of the invention, the polyisocyanate component is selected from polymeric MDI.
The organic polyisocyanates of the invention have an NCO content of 20 to 33 wt.%, preferably 25 to 32 wt.%, particularly preferably 30 to 32 wt.%. The NCO content was determined by GB/T12009.4-2016.
The organic polyisocyanates can also be used in the form of polyisocyanate prepolymers. These polyisocyanate prepolymers can be obtained by reacting an excess of the above organic polyisocyanate with a compound having at least two isocyanate-reactive groups at a temperature of, for example, 30 to 100 ℃, preferably about 80 ℃. The polyisocyanate prepolymers of the present invention have an NCO content of 20 to 33 wt.%, preferably 25 to 32 wt.%. The NCO content was determined by GB/T12009.4-2016.
A radical initiator refers to an agent capable of generating radicals in a radical reaction. Also known as free radical initiators. The process of generating free radicals becomes chain initiation. The radical initiator that can be used in the present invention includes, but is not limited to, peroxide initiators, organic peroxide initiators and inorganic peroxide initiators, azo initiators, redox initiators, and the like.
The general structural formula of the organic peroxide compound is R-O-O-H or R-O-O-R, wherein R is alkyl, acyl, carbonate and the like. It further comprises: acyl peroxides, for example: benzoyl peroxide, lauroyl peroxide; hydroperoxides, such as: cumene hydroperoxide, tert-butyl hydroperoxide; dialkyl peroxides, for example: di-tert-butyl peroxide, dicumyl peroxide; ester peroxides, tert-butyl peroxybenzoate, tert-butyl peroxypivalate; ketone peroxides, for example: methyl ethyl ketone peroxide and cyclohexanone peroxide; dicarbonate peroxides, for example: diisopropyl peroxydicarbonate and dicyclohexyl peroxydicarbonate. Generally, the order of activity of the organic peroxide is: dicarbonate peroxide > acyl peroxide > ester peroxide > dialkyl peroxide > hydroperoxide.
Azo initiators include azobisisobutyronitrile and azobisisoheptonitrile, which belong to low-activity initiators. Azodiisobutyronitrile is commonly used, the use temperature ranges from 50 ℃ to 65 ℃, the azodiisobutyronitrile is uniformly decomposed, only one free radical is formed, and other side reactions are avoided. Is relatively stable and can be safely stored in a pure state, but can be rapidly decomposed at 80-90 ℃. The disadvantage is the relatively low decomposition rate and the lack of dehydrogenation capability of the isobutyronitrile radicals formed, which cannot be used as initiators for graft polymerization.
In general, azobisisoheptonitrile has high activity and high initiation efficiency, and can be used for substituting azobisisobutyronitrile. And the azodiisobutyrate dimethyl ester (AIBME) has moderate initiation activity, easy control of polymerization reaction, no residue in the polymerization process, high product conversion rate and harmless decomposition products, and is the best substitute of azodiisobutyronitrile (AlBN). The decomposition temperature of the peroxide initiator and the azo initiator is high (50-100 ℃), so that the application of the low-temperature polymerization reaction is limited.
Free radical inhibitors useful in the present invention include hindered and/or conjugated structure containing phenols, amines and sulfur compounds, preferably hindered and/or conjugated structure containing phenols, amines and sulfur compounds which react with primary or chain free radicals to form non-free radical species or stable free radical species which are no longer capable of initiating polymerization of the monomers, more preferably hindered phenols, hindered amines and phenothiazines, and particularly preferably hindered phenols. Specifically, the compound includes phenols, amines or sulfur compounds having a hindered structure and/or a conjugated structure. Phenolic, amine or sulfur compounds containing hindered and/or conjugated structures, preferably those which react with primary or chain radicals to form non-radical species, or stable radical species which are no longer capable of initiating polymerization of the monomer, preferably phenolic, amine and sulfur compounds containing hindered and/or conjugated structures. The hindered phenol refers to a phenol compound having a sterically hindered structure, such as 2, 8-di-tert-butyl-4-methylphenol, tert-butylhydroquinone, and dibutylhydroxytoluene (also known as 2, 6-di-tert-butyl-p-cresol, abbreviated as BHT).
The hindered amine refers to a class of organic amine compounds with steric hindrance. Useful hindered amines include piperidine derivatives, imidazolone derivatives, and azacycloalkanone derivatives, for example, two main classes of 2, 2, 6, 6-tetramethylpiperidine derivatives and 1, 2, 2, 6, 6-pentamethylpiperidine derivatives. The method specifically comprises the following steps: benzoic acid (2, 2, 6, 6-tetramethyl-4-hydroxypiperidine) ester, sebacic acid bis (2, 2, 6, 6-tetramethyl-4-hydroxypiperidine) ester, nitrilotris [ acetic acid (2, 2, 6, 6-tetramethyl-4-hydroxypiperidine) ester ], and N, tris (1, 2, 2, 6, 6-pentamethyl-4-hydroxypiperidine) phosphite such as N' -bis (2, 2, 6, 6-tetramethylpiperidyl) hexamethylenediamine, bis (1, 2, 2, 6, 6-pentamethyl-4-hydroxypiperidine) sebacate, bis (1, 2, 2, 6, 6-pentamethyl-4-hydroxypiperidine) 2-ethyl-2- (4-hydroxy-3, 5-t-butylbenzyl) malonate, and the like.
The radical reaction inhibitor which can be used in the present invention further includes polymerization inhibitors and retarders, etc., such as p-methoxyphenol, benzoquinone, polymethylpyridine derivatives, low-valent copper ions, etc.
The polyol of the present invention may be a polyether polyol, a polyester polyol, a polycarbonate polyol and/or a mixture thereof. One or more polyether polyols are preferred, wherein at least one polyether polyol is an amine-initiated polyol. The polyether polyols have a functionality of from 2 to 8, preferably from 3 to 6, and a hydroxyl number of from 50 to 1200, preferably from 200 to 800.
Examples of polyether polyols which can be used in the present invention are aromatic amine-initiated polyether polyols, preferably propylene oxide-based polyether polyols initiated with diphenylmethanediamine.
A portion of the polyether polyols useful in the present invention are selected from sucrose, sorbitol initiated polyether polyols, more preferably, a portion of the polyether polyols are selected from sucrose, sorbitol initiated propylene oxide based polyether polyols.
The polyester polyol is prepared by reacting dicarboxylic acid or dicarboxylic anhydride with polyhydric alcohol. The dicarboxylic acid is preferably, but not limited to, aliphatic carboxylic acid containing 2 to 12 carbon atoms, such as: succinic acid, malonic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanecarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, and mixtures thereof. The dibasic acid anhydride is preferably, but not limited to, phthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, and mixtures thereof. The polyhydric alcohol is preferably, but not limited to, ethylene glycol, diethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, dipropylene glycol, 1, 3-methylpropylene glycol, 1, 4-butylene glycol, 1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, 1, 10-decanediol, glycerol, trimethylolpropane, or a mixture thereof. The polyester polyol also comprises polyester polyol prepared from lactone. The polyester polyol prepared from lactone is preferably, but not limited to, a polyester polyol prepared from epsilon-caprolactone.
The polycarbonate polyol is preferably, but not limited to, a polycarbonate diol. The polycarbonate diol may be prepared by reacting a diol with a dialkyl or diaryl carbonate or phosgene. The diol is preferably, but not limited to, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, diethylene glycol, trioxymethylene glycol, or a mixture thereof. The dialkyl or diaryl carbonate is preferably, but not limited to, diphenyl carbonate.
Optionally, the polyurethane composition of the invention also comprises one or more compounds B2 having the structure of formula (I)
Wherein R is1Selected from hydrogen, methyl or ethyl; r2Selected from alkylene groups having 2 to 6 carbon atoms; n is an integer selected from 1 to 6.
In a preferred embodiment of the invention, R2Selected from the group consisting of ethylene, propylene, butylene, pentylene, 1-methyl-1, 2-ethylene, 2-methyl-1, 2-ethylene, 1-ethyl-1, 2-ethylene, 2-ethyl-1, 2-ethylene, 1-methyl-1, 3-propylene, 2-methyl-1, 3-propylene, 3-methyl-1, 3-propylene, 1-ethyl-1, 3-propylene, 2-ethyl-1, 3-propylene, 3-ethyl-1, 3-propylene, 1-methyl-1, 4-butylene, 2-methyl-1, 4-butylene, 3-methyl-1, 4-butylene and 4-methyl-1, 4-butylene, 2-bis (4-phenylene) -propane, 1, 4-dimethylene-benzene, 1, 3-dimethylene-benzene, 1, 2-dimethylene-benzene.
Preferably, the B1) is selected from organic polyols, wherein the organic polyols are selected from polyols having a functionality of from 1.7 to 6, preferably from 1.9 to 4.5, and a hydroxyl number of 150-.
In a preferred embodiment of the invention, said B2) component is selected from: hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, or combinations thereof.
The compounds of formula (I) can be prepared by methods customary in the art, for example by (meth) acrylic anhydride or (meth) acrylic acid, (meth) acryloyl halide compounds with HO- (R)2O)n-H is prepared by esterification reactions, the preparation process being well known to the person skilled in the art, for example as described in handbook of polyurethane raw materials and auxiliaries (bang of liu yi jun, published 4/1/2005) third chapter, and chapter ii of polyurethane elastomers (bang of liu yi jun, published 8/2012), the entire contents of which are incorporated herein by reference.
In the method for producing a polyurethane resin of the present invention, in the addition polymerization reaction of an isocyanate group with a hydroxyl group, the isocyanate group may be an isocyanate group contained in an organic polyisocyanate (component a), or an isocyanate group contained in a reaction intermediate of the organic polyisocyanate (component a) with an organic polyol (B1) component) or B2) component, and the hydroxyl group may be a hydroxyl group contained in an organic polyol (B1) component) or B2) component, or a hydroxyl group contained in a reaction intermediate of the organic polyisocyanate (component a) with an organic polyol (B1) component) or B2) component.
The radical polymerization reaction of the present invention is an addition polymerization reaction of the olefinic bond, wherein the olefinic bond may be the olefinic bond contained in the B2) component or the olefinic bond contained in the intermediate product of the reaction of the B2) component with the organic polyisocyanate.
In the method for producing a polyurethane resin of the present invention, polyurethane addition polymerization (i.e., addition polymerization of isocyanate groups and hydroxyl groups) is carried out simultaneously with radical polymerization. As known to those skilled in the art, suitable reaction conditions can be selected so that the polyurethane addition polymerization reaction and the free radical polymerization reaction are carried out in sequence, but the polyurethane matrix prepared in the way is different from the polyurethane resin matrix prepared by simultaneously carrying out the polyurethane addition polymerization reaction and the free radical polymerization reaction, so that the mechanical properties and the manufacturability of the prepared polyurethane composite material are different.
Optionally, the polyurethane composition described above may also contain adjuvants or additives, including but not limited to: fillers, internal mold release agents, flame retardants, smoke suppressants, dyes, pigments, antistatic agents, antioxidants, UV stabilizers, diluents, defoamers, coupling agents, surface wetting agents, leveling agents, water scavengers, catalysts, molecular sieves, thixotropic agents, plasticizers, blowing agents, foam stabilizers, foam homogenizers, free radical reaction inhibitors or combinations thereof, which may optionally be comprised in the isocyanate component a) and/or the isocyanate-reactive component B) of the present invention. These components can also be stored separately as a further component and, when used for the preparation of polyurethane composites, are mixed with the isocyanate component A) and/or the component B) according to the invention before the preparation.
In some embodiments of the invention, the filler is selected from: aluminum hydroxide, bentonite, fly ash, wollastonite, perlite powder, cenosphere, calcium carbonate, talcum powder, mica powder, porcelain clay, fumed silica, expandable microspheres, diatomite, volcanic ash, barium sulfate, calcium sulfate, glass microspheres, stone powder, wood powder, sawdust, bamboo powder, bamboo sawdust, rice grains, straw scraps, sorghum straw scraps, graphite powder, metal powder, thermosetting composite material recycled powder, plastic particles or powder or a combination thereof. Wherein the glass microspheres can be solid or hollow.
The internal mold release agent which can be used in the present invention includes any conventional mold release agent used for producing polyurethane, and examples thereof include long-chain carboxylic acids, particularly fatty acids such as stearic acid, amines of long-chain carboxylic acids such as stearamide, fatty acid esters, metal salts of long-chain carboxylic acids such as zinc stearate, or polysiloxanes.
Examples of flame retardants that can be used in the present invention include triaryl phosphate, trialkyl phosphate, triaryl or trialkyl phosphate with halogen, melamine resins, halogenated paraffins, red phosphorus, or combinations thereof.
Other adjuvants useful in the present invention include water scavengers such as molecular sieves; defoamers, such as polydimethylsiloxane; coupling agents, such as monoepoxyethane or organic amine functional trialkoxysilane or combinations thereof. Coupling agents are particularly preferred for improving the adhesion of the resin matrix to the fibrous reinforcement. Finely particulate fillers, such as clays and fumed silicas, are commonly used as thixotropic agents.
Through repeated experiments, the method provided by the invention can provide the stably stored isocyanate composition, so that the polyurethane resin with excellent quality can be prepared, the process can be simplified, and the production efficiency can be improved.
Examples
The raw material type source is as follows:
isocyanate 44V 20: NCO%: 30.5-32.5%, viscosity: 160-240mP.s @25 ℃ as purchased from Corsia Polymer (China) Co., Ltd;
tert-butyl peroxybenzoate (TBPB): purchased from acyclovir;
tert-butylhydroquinone, dibutylhydroxytoluene (BHT): all purchased from Sigma-Aldrich;
GTS-THP gel time determinator: purchased from Shanghai Senlan scientific instruments, Inc.
Examples the test methods are illustrated below:
the NCO content, which is the NCO group content in the system, was determined by GB/T12009.4-2016.
The gel time is the time until the components of the reaction system start to be mixed until the viscosity reaches a certain value (for example, about 10000mPa. s). The gel time of the present invention is a time measured using a gel tester. The specific test method comprises the steps of uniformly mixing all components of the reaction system, placing the mixture in a gel tester, and recording the time from the pressing of an opening button to the stop of the gel tester, namely the gel time of the invention.
And (3) viscosity testing: tested according to GB/T12008.8-1992 standard.
Comparative example 1
100 parts by weight (pbw) of liquid isocyanate raw material 44V20 was added to a plastic cup, 2 parts by weight of TBPB was added thereto, the mixture was rapidly stirred uniformly, and then the mixture was put into an oven at 50 ℃ to monitor the viscosity change and temperature change. At intervals, samples were removed, cooled to room temperature (25 degrees Celsius), and tested for viscosity and NCO content. The test results are shown in Table 1.
TABLE 1 test results of comparative example 1
As can be seen from Table 1 above, the viscosity of the isocyanates increases significantly after a few weeks, already exceeding the normal quality standards. After 5 weeks, the NCO had dropped significantly and the viscosity had become too high to be useful.
The infrared spectrum of figure 1 also verifies these changes. Compared with the isocyanate without the addition of the free radical initiator, the isocyanate with the addition of the free radical initiator has three characteristic peaks (1704.80cm-1, 1409.60cm-1 and 758.36cm-1) after 56 days, shows the existence of the isocyanurate group, and verifies that the trimerization reaction is carried out under the existence of the free radical to generate the isocyanurate group.
(Note: FIG. 1, curve s1 shows the spectrum for the system only with isocyanate 44V 20; FIG. 1, curve s2 shows that the viscosity has not changed in the initial stage after 2pbw of TBPB has been added to isocyanate 44V 20; FIG. 1, curve s3 shows the spectrum after 56 days after 2pbw of TBPB has been added to isocyanate 44V 20.)
Example 1
Adding 100 parts by weight of liquid isocyanate raw material 44V20 into a plastic cup, adding 2 parts by weight of TBPB and 0.02 part by weight of tert-butyl hydroquinone, quickly stirring and dissolving uniformly, then placing into an oven at 50 ℃, and monitoring the viscosity change and the temperature change of the liquid isocyanate raw material. At intervals, samples were removed, cooled to room temperature (25 degrees Celsius), and tested for viscosity and NCO content. The test results are shown in Table 2.
TABLE 2 test results of example 1
Comparative example 2
Adding 100 parts by weight of liquid isocyanate raw material 44V20 into a plastic cup, adding 2 parts by weight of TBPB, quickly stirring uniformly, then placing into an oven at 60 ℃, and monitoring the viscosity change and the temperature change of the mixture. At intervals, samples were removed, cooled to room temperature (25 degrees Celsius), and tested for viscosity and NCO content. The test results are shown in Table 3.
TABLE 3 test results of comparative example 2
Example 2
100 parts by weight of liquid isocyanate 44V20 was added to a plastic cup, 2 parts by weight of TBPB and BHT as listed in Table 4 were added thereto, the mixture was rapidly stirred uniformly, and then the mixture was put into an oven at 60 ℃ with the temperature of the oven kept constant, and the viscosity change of the isocyanate mixture was monitored. At intervals, samples were removed, cooled to room temperature (25 degrees Celsius), and tested for viscosity and NCO content. The test results are shown in Table 4.
TABLE 4 test results of example 2
As can be seen from the above examples 1, 2 and comparative examples 1, 2, the storage and transportation stability of the isocyanate containing a radical initiator can be greatly improved by adding a small amount of a radical inhibitor to the isocyanate, and the shelf life of the product can be effectively improved.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (15)
1. A method for stably storing an isocyanate composition comprising:
A1) one or more polyisocyanates;
A2) at least one free radical initiator;
which is the addition of component A3) at least one free-radical inhibitor to the isocyanate composition.
2. The process as claimed in claim 1, wherein the polyisocyanate is selected from aromatic isocyanates, preferably diphenylmethane diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate or combinations thereof, particularly preferably diphenylmethane diisocyanate or (poly) diphenylmethane diisocyanate.
3. Process according to claim 1 or 2, characterized in that the a2) free radical initiator is present in an amount of 0.1 to 5pbw, preferably 0.2 to 4pbw, more preferably 0.4 to 3pbw, based on the total weight of the isocyanate composition, based on 100 pbw.
4. Process according to claim 1 or 2, characterized in that the a3) free radical inhibitor is present in an amount of 0.001 to 2.0pbw, preferably 0.002 to 1pbw, more preferably 0.01 to 0.8pbw, based on the total weight of the isocyanate composition, based on 100 pbw.
5. The method according to claim 1 or 2, wherein a3) the radical inhibitor is selected from the group consisting of phenols, amines and sulfur compounds containing hindered and/or conjugated structures, preferably hindered phenols, hindered amines and phenothiazines, more preferably hindered phenols.
6. An isocyanate composition comprising the following components:
A1) one or more polyisocyanates;
A2) a free radical initiator; and
A3) at least one free radical inhibitor.
7. A process for preparing (poly) isocyanurates by reacting an isocyanate composition comprising:
A1) one or more polyisocyanates;
A2) a free radical initiator; and
A3) at least one free radical inhibitor.
8. Use of a free radical inhibitor for inhibiting the preparation of (poly) isocyanurates by the trimerization of isocyanates catalyzed by a free radical initiator.
9. Use according to claim 8, wherein the free radical inhibitor is present in an amount of 0.001 to 2.0pbw, preferably 0.002 to 1pbw, more preferably 0.01 to 0.8pbw, based on 100pbw of the total weight of the isocyanate composition.
10. A method for preparing polyurethane resin, which comprises the following steps of reacting a polyurethane reaction system comprising the following components:
component A) comprising:
A1) one or more polyisocyanates;
A2) a free radical initiator;
A3) at least one free radical inhibitor;
component B) comprising:
B1) one or more organic polyols in an amount of 21 to 60 wt.%, based on the total weight of the polyurethane composition in 100 wt.%;
B2) one or more compounds having the structure of formula (I)
Wherein R1 is selected from hydrogen, methyl or ethyl; r2 is selected from alkylene having 2 to 6 carbon atoms, 2-bis (4-phenylene) -propane, 1, 4-bis (methylene) benzene, 1, 3-bis (methylene) benzene, 1, 2-bis (methylene) benzene; n is an integer selected from 1 to 6.
11. The method as set forth in claim 10, wherein said B2) component is selected from the group consisting of: hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, or combinations thereof.
12. The process as claimed in claim 10 or 11, wherein the organic polyol is selected from the group consisting of polyols having a functionality of from 1.7 to 6, preferably from 1.9 to 4, more preferably from 1.9 to 2.8, and a hydroxyl number of from 150 to 1100 mgKOH/g.
13. A polyurethane resin obtained by the method for producing a polyurethane resin according to claims 10 to 12.
14. A polyurethane product comprising the polyurethane resin of claim 13.
15. The polyurethane product of claim 14, wherein the polyurethane product is selected from the group consisting of cable trays, window and door curtain frames, ladder frames, tent poles or tubes, antiglare panels, flooring, sucker rods, utility poles and crossarms, guard rails, grilles, architectural profiles, container profiles and sheets, bicycle frames, fishing poles, cable cores, insulator mandrels, radome, single or sandwich continuous sheets, and leaf shells, webs, caps, joists, and blade roots of turbofan blades.
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| CN202010834506.8A CN114075318A (en) | 2020-08-18 | 2020-08-18 | Method for stably storing isocyanurate composition |
| PCT/EP2021/072397 WO2022038015A1 (en) | 2020-08-18 | 2021-08-11 | A method for stably storing an isocyanurate composition |
| CN202180056370.5A CN116171296A (en) | 2020-08-18 | 2021-08-11 | Method for stably storing isocyanurate composition |
| EP21758688.2A EP4200345A1 (en) | 2020-08-18 | 2021-08-11 | A method for stably storing an isocyanurate composition |
| US18/014,190 US20230303801A1 (en) | 2020-08-18 | 2021-08-11 | A method for stably storing an isocyanurate composition |
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