CN115894302A - Process for the preparation of biuret polyisocyanates - Google Patents
Process for the preparation of biuret polyisocyanates Download PDFInfo
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- CN115894302A CN115894302A CN202211286198.5A CN202211286198A CN115894302A CN 115894302 A CN115894302 A CN 115894302A CN 202211286198 A CN202211286198 A CN 202211286198A CN 115894302 A CN115894302 A CN 115894302A
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- Prior art keywords
- water
- biuret polyisocyanate
- absorbing resin
- polyvinyl alcohol
- acid
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- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000005056 polyisocyanate Substances 0.000 title claims abstract description 52
- 229920001228 polyisocyanate Polymers 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 85
- 229920005989 resin Polymers 0.000 claims abstract description 83
- 239000011347 resin Substances 0.000 claims abstract description 83
- 239000002250 absorbent Substances 0.000 claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 26
- 239000000178 monomer Substances 0.000 claims abstract description 25
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 24
- 230000002378 acidificating effect Effects 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 238000010521 absorption reaction Methods 0.000 claims abstract description 11
- 239000000376 reactant Substances 0.000 claims abstract description 10
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000002808 molecular sieve Substances 0.000 claims description 42
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 37
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 37
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 22
- 239000002131 composite material Substances 0.000 claims description 20
- 239000003431 cross linking reagent Substances 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 8
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 claims description 7
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 6
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 6
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 5
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 229940047670 sodium acrylate Drugs 0.000 claims description 4
- ZJQIXGGEADDPQB-UHFFFAOYSA-N 1,2-bis(ethenyl)-3,4-dimethylbenzene Chemical group CC1=CC=C(C=C)C(C=C)=C1C ZJQIXGGEADDPQB-UHFFFAOYSA-N 0.000 claims description 3
- IGDCJKDZZUALAO-UHFFFAOYSA-N 2-prop-2-enoxypropane-1,3-diol Chemical compound OCC(CO)OCC=C IGDCJKDZZUALAO-UHFFFAOYSA-N 0.000 claims description 3
- CCTFMNIEFHGTDU-UHFFFAOYSA-N 3-methoxypropyl acetate Chemical compound COCCCOC(C)=O CCTFMNIEFHGTDU-UHFFFAOYSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000004386 diacrylate group Chemical group 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 150000002894 organic compounds Chemical class 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- -1 propoxyglyceryl Chemical group 0.000 claims description 3
- 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 claims description 3
- 238000004064 recycling Methods 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 15
- 238000003786 synthesis reaction Methods 0.000 abstract description 10
- 229920002396 Polyurea Polymers 0.000 abstract description 7
- 239000006227 byproduct Substances 0.000 abstract description 5
- 239000002244 precipitate Substances 0.000 abstract description 3
- 230000035945 sensitivity Effects 0.000 abstract description 3
- 239000003377 acid catalyst Substances 0.000 abstract description 2
- 230000002745 absorbent Effects 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 102100023792 ETS domain-containing protein Elk-4 Human genes 0.000 description 8
- 101710130332 ETS domain-containing protein Elk-4 Proteins 0.000 description 8
- 101710138742 Receptor-type tyrosine-protein phosphatase H Proteins 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 102100023794 ETS domain-containing protein Elk-3 Human genes 0.000 description 3
- 101800001701 Saposin-C Proteins 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 101000704903 Saponaria officinalis Ribosome-inactivating protein saporin-6 Proteins 0.000 description 2
- 101000704901 Saponaria officinalis Ribosome-inactivating protein saporin-7 Proteins 0.000 description 2
- XLXOGJYARRBRPZ-UHFFFAOYSA-N [2,3-di(prop-2-enoyloxy)-3-propoxypropyl] prop-2-enoate Chemical compound CCCOC(OC(=O)C=C)C(OC(=O)C=C)COC(=O)C=C XLXOGJYARRBRPZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 description 2
- HVBMYHDTXIDFKE-UHFFFAOYSA-N diethyl hydrogen phosphate;ethyl dihydrogen phosphate Chemical compound CCOP(O)(O)=O.CCOP(O)(=O)OCC HVBMYHDTXIDFKE-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 102100023364 Ganglioside GM2 activator Human genes 0.000 description 1
- 101710201362 Ganglioside GM2 activator Proteins 0.000 description 1
- 238000003109 Karl Fischer titration Methods 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 101000704910 Saponaria officinalis Ribosome-inactivating protein saporin-4 Proteins 0.000 description 1
- 101000704905 Saponaria officinalis Ribosome-inactivating protein saporin-5 Proteins 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000000199 molecular distillation Methods 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000035440 response to pH Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical group OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000008400 supply water Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a preparation method of biuret polyisocyanate, which comprises the following steps: providing a water-absorbing resin and making the water-absorbing resin absorb water to saturation, wherein the strength of the water-absorbing resin is greater than or equal to 2000N/kg, the water absorption is 2000g/g, the water-absorbing resin can release absorbed water molecules under an acidic condition, and the speed of releasing the water molecules is 0.10 g/(g.h) -0.15 g/(g.h); mixing saturated water-absorbing resin, diisocyanate monomer and acid catalyst to form a reaction system, and reacting to obtain a reactant; separating biuret polyisocyanate from the reaction product. According to the invention, saturated water-absorbent resin is adopted to release water molecules as required in the reaction process to participate in the synthesis of the biuret polyisocyanate, the generation of polyurea byproducts can be inhibited, the reaction selectivity is further improved, no precipitate is generated in the reaction process, the problem of blockage of equipment and pipelines is avoided, the stability and the sensitivity to a solvent of the biuret polyisocyanate are obviously improved, and the viscosity of the biuret polyisocyanate is improved.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of biuret polyisocyanate.
Background
The preparation process of biuret polyisocyanates can be broadly divided into the aqueous and amine processes, wherein the aqueous preparation of biuret polyisocyanates generally has good monomer stability, good dilutability and excellent color values compared to the amine process. However, since water and diisocyanate monomers are not mutually soluble, the concentration of water on the oil/water contact surface is too high during the synthesis process, which easily causes the generation of polyurea byproducts, thereby causing the problems of reduced reaction selectivity, increased product viscosity, blockage of equipment and pipelines due to insoluble substances, and the like.
In order to avoid excessive concentrations of water at the oil/water interface, patent DE1101394 discloses the addition of water in the form of crystal water, hydrates or reaction-forming water, such as water produced when salicylic acid forms polysalicylic acid under the reaction conditions, to supply water to the reaction system, but this process is uneconomical and not industrially feasible. Patent JP 19740565656328 discloses a method of adding a mixed solvent, but the solvent separation brings about problems of high energy consumption, high VOC, solvent residue, and the like, which affect the product quality. Patent US5641851 discloses that the addition of acid compounds suppresses the formation of insoluble urea, but this method only ameliorates the formation of polyurea and does not completely eradicate the formation of polyurea. Patent JP2000516287A5 discloses a method for synthesizing biuret under the condition of vigorous stirring, but the method has high energy consumption, high requirement on equipment, large equipment loss and limited production scale. Patent nos. CN102321231A and CN111217972A disclose that different compounds of water of crystallization react with hexamethylene diisocyanate, but the amount of water in the compounds of water of crystallization is relatively small, so that the amount of the compounds of water of crystallization used in the reaction is large, and the reaction is difficult.
Disclosure of Invention
In view of the above, it is necessary to provide a method for producing biuret polyisocyanates, which employs a saturated water-absorbent resin as a water donor, releases water molecules as needed during the reaction to participate in the synthesis of biuret polyisocyanates, and can suppress the formation of polyurea by-products.
A method for preparing biuret polyisocyanates, comprising the steps of:
providing a water-absorbing resin and enabling the water-absorbing resin to absorb water to be saturated, wherein the strength of the water-absorbing resin is greater than or equal to 2000N/kg, the water absorption rate is greater than or equal to 2000g/g, the water-absorbing resin can release absorbed water molecules under an acidic condition, and the speed of releasing the water molecules is 0.10 g/(g.h) -0.15 g/(g.h);
mixing the saturated water-absorbent resin, a diisocyanate monomer and an acidic catalyst to form a reaction system, and reacting to obtain a reactant; and
separating biuret polyisocyanate from the reaction product.
In one embodiment, the size of the water absorbent resin is less than or equal to 20 mesh.
In one embodiment, the amount of the saturated water-absorbing resin in the reaction system is 2-5% of the mass of the diisocyanate monomer;
and/or the dosage of the acidic catalyst is 0.01-1% of the mass of the diisocyanate monomer.
In one embodiment, the water-absorbing resin is selected from polyvinyl alcohol copolymer-molecular sieve composite water-absorbing resins.
In one embodiment, in the polyvinyl alcohol copolymer-molecular sieve composite water absorbent resin, the polyvinyl alcohol copolymer is formed by reacting polyvinyl alcohol, a comonomer and a crosslinking agent, wherein the comonomer is selected from at least two of acrylonitrile, sodium acrylate, acrolein, acrylamide, polyethylene glycol diacrylate, propoxy glycerol triacrylate and maleic anhydride, and the crosslinking agent is selected from organic compounds containing at least two groups of double bonds, hydroxyl groups, amine groups, imino groups, carboxyl groups and epoxy groups.
In one embodiment, the cross-linking agent is selected from at least one of ethylene glycol, glycerol, trimethylolpropane, N-methylenebisacrylamide, glycerol allyl ether, N-methylolacrylamide, glycidyl methacrylate, glycidyl acrylate, hexamethylenediamine, adipic acid, phthalic acid, divinylxylene.
In one embodiment, the mass ratio of the comonomer to the polyvinyl alcohol is 0.2 to 1.5, and the mass ratio of the crosslinking agent to the polyvinyl alcohol is 0.001 to 0.05.
In one embodiment, in the polyvinyl alcohol copolymer-molecular sieve composite water absorbent resin, the pore diameter of the molecular sieve is 8nm-20nm, and the mass fraction of the molecular sieve in the polyvinyl alcohol copolymer-molecular sieve composite water absorbent resin is 5% -15%.
In one embodiment, the molecular sieve is selected from at least one of MCM series molecular sieves, SBA-n series molecular sieves, MSU-X series molecular sieves.
In one embodiment, the diisocyanate monomer is selected from at least one of an aliphatic diisocyanate or a cycloaliphatic diisocyanate.
In one embodiment, the diisocyanate monomer is at least one selected from isophorone diisocyanate and hexamethylene diisocyanate.
In one embodiment, the acidic catalyst is selected from at least one of phosphoric acid, phosphoric acid ethyl ester, phosphoric acid diethyl ester, sulfonic acid, oxalic acid, formic acid, acetic acid, propionic acid, butyric acid, pivalic acid.
In one embodiment, a solubilizer is further added into the reaction system, the amount of the solubilizer is 5% -10% of the mass of the diisocyanate monomer, and the solubilizer is selected from at least one of triethyl phosphate, dimethylformamide and methoxypropyl acetate.
In one embodiment, in the step of reacting the reaction system, the temperature is raised to a first temperature and maintained for 1 hour to 4 hours, and then raised to a second temperature and maintained for 1 hour to 4 hours, wherein the first temperature is 90 ℃ to 130 ℃, the second temperature is 110 ℃ to 150 ℃, and the second temperature is higher than the first temperature.
In one embodiment, in the step of separating the biuret polyisocyanate from the reactant, the water-absorbent resin is also recovered and is made to absorb water again to saturation for recycling in the reaction system.
The water-absorbing resin of the invention has the following characteristics: firstly, the water with more than 2000 times of self weight can be absorbed and stored in a resin molecule cross-linked framework, and the water absorption performance is excellent; secondly, the water-absorbing resin has responsiveness to pH, can cause dissociation of hydrophilic groups on the water-absorbing resin under an acidic condition, and can cause skeleton contraction caused by water absorption expansion, so that the water-absorbing resin releases water molecules stored in a molecular grid, and the speed of releasing the water molecules can be automatically adjusted according to ionic strength; thirdly, the strength is high, and the material is not easy to break.
Therefore, in the preparation method of the present invention, when the saturated water-absorbent resin is used as a donor of water, and is mixed with the diisocyanate monomer and the acidic catalyst to form a reaction system, the saturated water-absorbent resin can be suspended in the reaction system and can release water molecules under acidic conditions, and the released water molecules can immediately participate in the synthesis of the biuret polyisocyanate. Therefore, by controlling the speed of releasing water molecules of the saturated water-absorbent resin under the acidic condition, the synthesis efficiency of the biuret polyisocyanate can be ensured, the water molecules at any position of a reaction system can be kept at a lower concentration in the whole synthesis process of the biuret polyisocyanate, the formation of polyurea byproducts is further inhibited, the selectivity of the reaction is improved, no precipitate is generated in the reaction process, the phenomenon that equipment and pipelines are blocked is avoided, meanwhile, the stability and the sensitivity to a solvent of the generated biuret polyisocyanate can be obviously improved, and the viscosity of the biuret polyisocyanate is improved.
Detailed Description
In order to facilitate an understanding of the present invention, the present invention will be described in more detail below. It should be understood, however, that the present invention may be embodied in many different forms and should not be construed as being limited to the embodiments or examples set forth herein. Rather, these embodiments or examples are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments or examples only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of two or more of the associated listed items, including any and all combinations of two or more of the associated listed items, or all of the associated listed items.
The preparation method of the biuret polyisocyanate provided by the invention comprises the following steps:
s1, providing a water-absorbent resin and making the water-absorbent resin absorb water to saturation, wherein the strength of the water-absorbent resin is greater than or equal to 2000N/kg, the water absorption rate is greater than or equal to 2000g/g, the water-absorbent resin can release absorbed water molecules under an acidic condition, and the speed of releasing the water molecules is 0.10 g/(g.h) -0.15 g/(g.h);
s2, mixing the saturated water-absorbent resin, a diisocyanate monomer and an acid catalyst to form a reaction system, and reacting to obtain a reactant;
and S3, separating the reactants to obtain the biuret polyisocyanate.
The preparation method of the biuret polyisocyanate provided by the invention is a water method, and is different from the traditional water method in that the saturated water-absorbent resin is adopted as a water donor, and the properties of water absorption rate, strength, water releasing speed under acidic conditions and the like of the water-absorbent resin are regulated, so that the saturated water-absorbent resin is suspended in a reaction system and can release water molecules under acidic conditions, and the released water molecules can immediately participate in the synthesis of the biuret polyisocyanate, namely the process of releasing water molecules from the saturated water-absorbent resin and the process of reacting the water molecules with diisocyanate monomers are simultaneously and continuously carried out.
Therefore, by controlling the speed of releasing water molecules of the saturated water-absorbent resin under the acidic condition, the synthesis efficiency of the biuret polyisocyanate can be ensured, the water molecules at any position of a reaction system can be maintained at a lower concentration in the whole synthesis process of the biuret polyisocyanate, the formation of polyurea byproducts is further inhibited, the selectivity of the reaction is improved, no precipitate is generated in the reaction process, the phenomenon that equipment and pipelines are blocked is avoided, the stability and the sensitivity to a solvent of the generated biuret polyisocyanate can be obviously improved, and the viscosity of the biuret polyisocyanate is improved.
The type of the water-absorbent resin is not limited in the present invention, and the water-absorbent resin may satisfy performance requirements such as water absorption, strength, response to pH, and release rate of water under acidic conditions.
In one or more embodiments, the water absorbent resin in step S1 is selected from polyvinyl alcohol-based water absorbent resins, preferably polyvinyl alcohol copolymer-molecular sieve composite water absorbent resins.
Optionally, the water absorption rate, strength, water release speed under acidic conditions and other properties of the polyvinyl alcohol copolymer-molecular sieve composite water absorbent resin can be adjusted by adjusting the pore size of the molecular sieve in the polyvinyl alcohol copolymer-molecular sieve composite water absorbent resin, the comonomer, the cross-linking agent, the cross-linking density and the like of the polyvinyl alcohol copolymer.
In one or more embodiments, in the polyvinyl alcohol copolymer-molecular sieve composite water absorbent resin, the polyvinyl alcohol copolymer is formed by reacting polyvinyl alcohol, a comonomer and a crosslinking agent.
Wherein the mass ratio of the comonomer to the polyvinyl alcohol is 0.2-1.5, and the comonomer is selected from at least two of acrylonitrile, sodium acrylate, acrolein, acrylamide, polyethylene glycol diacrylate, propoxy glycerol triacrylate and maleic anhydride.
Wherein the mass ratio of the cross-linking agent to the polyvinyl alcohol is 0.001-0.05, the cross-linking agent is selected from organic compounds containing at least two groups of double bonds, hydroxyl groups, amine groups, imino groups, carboxyl groups and epoxy groups, and optionally, the cross-linking agent is selected from at least one of ethylene glycol, glycerol, trimethylolpropane, N-methylene bisacrylamide, glycerol allyl ether, N-hydroxymethyl acrylamide, glycidyl methacrylate, glycidyl acrylate, hexamethylene diamine, adipic acid, phthalic acid and divinyl xylene.
In one or more embodiments, the pore size of the molecular sieve in the polyvinyl alcohol copolymer-molecular sieve composite water absorbent resin is 8nm to 20nm, and the mass fraction of the molecular sieve in the polyvinyl alcohol copolymer-molecular sieve composite water absorbent resin is 5% to 15%, and more preferably 9% to 15%.
Optionally, the molecular sieve is selected from at least one of MCM series molecular sieves, SBA-n series molecular sieves and MSU-X series molecular sieves.
Optionally, the preparation method of the polyvinyl alcohol graft copolymer-molecular sieve composite water-absorbent resin comprises the following steps:
(1) Mixing polyvinyl alcohol, a comonomer, a crosslinking agent and a molecular sieve to obtain a first preparation, wherein the mass ratio of the polyvinyl alcohol to the comonomer to the crosslinking agent to the molecular sieve is 1 (0.2-1.5) to 0.001-0.05) to 0.1-0.3;
(2) Deoxidizing the first preparation by adopting a protective atmosphere such as nitrogen and the like, and then standing for 12-72 hours at the temperature of-20-30 ℃ to obtain a second preparation;
(3) Placing the second preparation in a cobalt source chamber for grafting reaction to obtain a reaction product, wherein the radiation intensity of a cobalt source is 10Kgy/min-100Kgy/min, and the time is 1 hour-10 hours;
(4) And hydrolyzing the reaction product, cleaning after the hydrolysis is finished, and drying to constant weight to obtain the polyvinyl alcohol copolymer-molecular sieve composite water-absorbent resin, wherein the hydrolysis condition is selected from a methanol solution of sodium hydroxide, and the reaction product can be cut and thinned before the hydrolysis.
In one or more embodiments, the water absorbent resin has a size of 20 mesh or less, which facilitates dispersion of the water absorbent resin in the reaction system.
In the step S2, the saturated water-absorbing resin, a diisocyanate monomer and an acidic catalyst are mixed to form a reaction system, wherein the amount of the saturated water-absorbing resin is 2-5% of the mass of the diisocyanate monomer, and the amount of the acidic catalyst is 0.01-1% of the mass of the diisocyanate monomer.
Wherein the diisocyanate monomer is selected from at least one of aliphatic diisocyanate or alicyclic diisocyanate, including hexamethylene diisocyanate, 1, 4-cyclohexane diisocyanate, 4' -dicyclohexylmethane diisocyanate, isophorone diisocyanate and the like, preferably, the diisocyanate monomer is selected from at least one of isophorone diisocyanate and hexamethylene diisocyanate; the acidic catalyst is at least one selected from phosphoric acid, phosphoric acid ethyl ester, phosphoric acid diethyl ester, sulfonic acid, oxalic acid, formic acid, acetic acid, propionic acid, butyric acid and pivalic acid.
In order to increase the mutual solubility effect of the diisocyanate monomer and water, in one or more embodiments, a solubilizing agent is further added to the reaction system, the amount of the solubilizing agent is 5% -10% of the mass of the diisocyanate monomer, and the solubilizing agent is selected from at least one of triethyl phosphate, dimethylformamide and methoxypropyl acetate.
In one or more embodiments, in the step of reacting the reaction system, the temperature is raised to a first temperature and maintained for 1 hour to 4 hours, and then raised to a second temperature and maintained for 1 hour to 4 hours, wherein the first temperature is 90 ℃ to 130 ℃, the second temperature is 110 ℃ to 150 ℃, and the second temperature is higher than the first temperature.
The reaction system is reacted under normal pressure, after the temperature is maintained at the first temperature for 1 hour to 4 hours, redundant gas in the reactor is discharged, the pressure is recovered to the normal pressure, and then the temperature is continuously increased to the second temperature for the heat-preservation reaction.
In step S3, the separation of biuret polyisocyanate from the reactants may be by rectification or the like.
In the step of separating and obtaining biuret polyisocyanate from the reactant, the water-absorbent resin can be recovered, and the recovered water-absorbent resin can absorb water again to saturation and can be recycled in the reaction system, so that the production cost is reduced.
Hereinafter, the preparation method of the biuret polyisocyanate will be further illustrated by the following specific examples.
Preparation example of polyvinyl alcohol copolymer-molecular Sieve composite Water-absorbent resin
Preparation method of SAP-1:
(1) 100 parts by mass of polyvinyl alcohol is dissolved in hot water/toluene at 90 ℃, then cooled to room temperature, 60 parts by mass of sodium acrylate, 90 parts by mass of propoxyglyceryl triacrylate, 2 parts by mass of N-methylolacrylamide and 15 parts by mass of MCM-22 molecular sieve are added, and the mixture is fully stirred to obtain a first preparation.
(2) Introducing N into the first preparation 2 After deoxygenation, the mixture was allowed to stand at 5 ℃ for 24 hours to give a second formulation.
(3) And placing the second preparation in a cobalt source chamber, and carrying out graft copolymerization reaction for 6 hours at room temperature with the radiation intensity of 50Kgy/min to obtain a reaction product.
(4) And taking out the reaction product, cutting the reaction product into 5mm slices, soaking the slices in a methanol solution of NaOH for hydrolysis, washing the slices with anhydrous methanol for three times after the hydrolysis is finished, then drying the slices in vacuum at 120 ℃ for 24 hours to constant weight, crushing the slices, and sieving the slices with a 20-mesh sieve to obtain the polyvinyl alcohol copolymer-molecular sieve composite water-absorbent resin SAP-1.
The preparation methods of the polyvinyl alcohol copolymer-molecular sieve composite water-absorbent resins SAP-2 to SAP-6 were the same as those of SAP-1 except that the reaction control parameters were different, and the specific reaction parameters and reaction results were shown in tables 1 and 2, and similarly, the preparation methods of the comparative polyvinyl alcohol copolymer-molecular sieve composite water-absorbent resins SAP-7 to SAP-11 were the same as those of SAP-1 except that the reaction control parameters were different, and the specific reaction parameters and reaction results were shown in tables 1 and 2.
Wherein the test standard of the water absorption rate is as follows: weighing 1.0g of water-absorbent resin, putting the water-absorbent resin into 5000mL of distilled water, standing for 12 hours until the water-absorbent resin fully absorbs water, filtering excessive water by using a 100-mesh nylon mesh bag, and weighing the weight after water absorption.
The test criteria for strength were: the saturated water-absorbent resin was placed in a compressor, the limit pressure was measured by an INSTRON-1121 type material testing machine, a 20-mesh sieve was covered on the bottom of the sample cell, the saturated water-absorbent resin was extruded at a speed of 5mm/min, and the compression limit force at which the water-absorbent resin started to be extruded was measured.
The test criteria for the rate of water molecule release were: adding 20g of saturated water-absorbent resin and 50g of 10wt% ethanol solution of pivalic acid into a round-bottom flask in sequence, and stirring at the rotating speed of 300 rpm; samples were taken every 30min and the water content of the samples was determined by karl fischer titration.
TABLE 1
TABLE 2
Preparation experiment of biuret polyisocyanates:
example 1
The SAP-1 is added into deionized water, stirred for one hour and filtered to obtain saturated SAP-1.
Into a reaction kettle were sequentially charged 700 parts by mass of Hexamethylene Diisocyanate (HDI), 5 parts by mass of pivalic acid (PVA), 50 parts by mass of triethyl phosphate (TEP) and 30 parts by mass of saturated SAP-1 to obtain a reaction system.
Setting a temperature raising program to raise the temperature in the reaction kettle to 120 ℃ within 60min, then preserving the heat for 2 hours, keeping the heating state, discharging the redundant gas in the kettle, continuing to raise the temperature to 145 ℃ after the normal pressure is recovered, preserving the heat for 2 hours, reducing the temperature to 25 ℃ after the reaction is finished, stopping stirring, discharging the reactant, and filtering to remove the water-absorbent resin.
The reaction solution was passed through a two-stage molecular distillation apparatus at a rate of 0.5kg/h, and biuret polyisocyanate (HDI biuret) was obtained by separation and purification. Wherein the temperature of a hot plate of the primary separation device is controlled at 100 ℃, the temperature of a cold plate is controlled at 10 ℃, and the vacuum degree is 100Pa; the temperature of a hot plate of the secondary separation device is controlled at 135 ℃, the temperature of a cold plate is controlled at 5 ℃, and the vacuum degree is 10Pa.
Examples 2 to 6
Examples 2 to 6 are different from example 1 in that the water-absorbent resins used were SAP-2, SAP-3, SAP-4, SAP-5 and SAP-6, respectively, and the rest of the procedure was the same as in example 1.
Example 7
Example 7 differs from example 1 in that 35 parts by mass of saturated SAP-1 are added and the procedure is otherwise the same as in example 1.
Example 8
Example 8 differs from example 1 in that the catalyst used, pivalic acid, was changed to methanesulfonic acid.
Comparative examples 1 to 5
Comparative examples 1 to 5 are different from example 1 in that the water-absorbent resins used are SAP-7 to SAP-11, respectively.
Comparative example 6
Comparative example 6 is different from example 1 in that water is supplied dropwise to the reaction system.
The reaction effects of examples 1 to 8 and comparative examples 1 to 6 are shown in Table 3.
TABLE 3
The cyclic application test of the polyvinyl alcohol copolymer-molecular sieve composite water-absorbent resin comprises the following steps:
the filtered SAP-2 of example 2 was subjected to a mechanical application experiment for preparing biuret polyisocyanate, and the data are shown in table 4 below, and the specific preparation procedure of biuret polyisocyanate was the same as that of example 2.
TABLE 4
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent should be subject to the appended claims.
Claims (15)
1. A preparation method of biuret polyisocyanate is characterized by comprising the following steps:
providing a water-absorbing resin and making the water-absorbing resin absorb water to saturation, wherein the strength of the water-absorbing resin is greater than or equal to 2000N/kg, the water absorption rate is greater than or equal to 2000g/g, the water-absorbing resin can release absorbed water molecules under an acidic condition, and the speed of releasing the water molecules is 0.10 g/(g.h) -0.15 g/(g.h);
mixing the saturated water-absorbent resin, a diisocyanate monomer and an acidic catalyst to form a reaction system, and reacting to obtain a reactant; and
separating biuret polyisocyanate from the reaction product.
2. The method for producing biuret polyisocyanate according to claim 1, characterized in that the size of said water-absorbing resin is less than or equal to 20 mesh.
3. The method for preparing biuret polyisocyanate according to claim 1, characterized in that the amount of the saturated water-absorbing resin used in the reaction system is 2% -5% by mass of the diisocyanate monomer;
and/or the dosage of the acidic catalyst is 0.01-1% of the mass of the diisocyanate monomer.
4. The method for preparing biuret polyisocyanates according to any of claims 1-3, characterized in that said water-absorbing resin is selected from polyvinyl alcohol copolymer-molecular sieve composite water-absorbing resins.
5. The method for preparing biuret polyisocyanate according to claim 4, wherein the polyvinyl alcohol copolymer is prepared by reacting polyvinyl alcohol, comonomer and cross-linking agent, wherein the comonomer is selected from at least two of acrylonitrile, sodium acrylate, acrolein, acrylamide, polyethylene glycol diacrylate, propoxyglyceryl triacrylate and maleic anhydride, and the cross-linking agent is selected from organic compounds containing at least two groups of double bond, hydroxyl group, amine group, imino group, carboxyl group and epoxy group.
6. The method for producing a biuret polyisocyanate according to claim 5, characterized in that said crosslinking agent is selected from at least one of ethylene glycol, glycerol, trimethylolpropane, N-methylenebisacrylamide, glycerol allyl ether, N-methylolacrylamide, glycidyl methacrylate, glycidyl acrylate, hexamethylenediamine, adipic acid, phthalic acid, divinylxylene.
7. The method for producing a biuret polyisocyanate according to claim 5, characterized in that the mass ratio of the comonomer to the polyvinyl alcohol is from 0.2 to 1.5, and the mass ratio of the crosslinking agent to the polyvinyl alcohol is from 0.001 to 0.05.
8. The preparation method of biuret polyisocyanate according to claim 4, characterized in that in the polyvinyl alcohol copolymer-molecular sieve composite water-absorbent resin, the pore diameter of the molecular sieve is 8nm-20nm, and the mass fraction of the molecular sieve in the polyvinyl alcohol copolymer-molecular sieve composite water-absorbent resin is 5% -15%.
9. The method for producing a biuret polyisocyanate according to claim 8, characterized in that said molecular sieve is selected from at least one of MCM series molecular sieves, SBA-n series molecular sieves, MSU-X series molecular sieves.
10. The method for preparing biuret polyisocyanate according to claim 4, characterized in that said diisocyanate monomer is selected from at least one of aliphatic diisocyanates or cycloaliphatic diisocyanates.
11. The method for preparing biuret polyisocyanate according to claim 10, characterized in that the diisocyanate monomer is selected from at least one of isophorone diisocyanate and hexamethylene diisocyanate.
12. The method for preparing biuret polyisocyanate according to claim 4, characterized in that said acidic catalyst is selected from at least one of phosphoric acid, phosphoethyl ester, phosphodiethyl ester, sulfonic acid, oxalic acid, formic acid, acetic acid, propionic acid, butyric acid, pivalic acid.
13. The method for preparing biuret polyisocyanate according to claim 4, characterized in that a solubilizer is added into the reaction system, the amount of the solubilizer is 5% -10% of the mass of the diisocyanate monomer, and the solubilizer is selected from at least one of triethyl phosphate, dimethylformamide and methoxypropyl acetate.
14. The method for preparing biuret polyisocyanate according to claim 4, wherein said reaction system is heated to a first temperature and maintained for 1-4 hours, and then heated to a second temperature and maintained for 1-4 hours, wherein said first temperature is 90-130 ℃, said second temperature is 110-150 ℃, and said second temperature is higher than said first temperature.
15. The method for preparing biuret polyisocyanate according to claim 4, characterized in that in the step of separating biuret polyisocyanate from the reactants, the water-absorbent resin is also recovered and is made to absorb water again to saturation for recycling in the reaction system.
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| DE1101394B (en) * | 1958-04-24 | 1961-03-09 | Bayer Ag | Process for the production of polyisocyanates with a biuret structure |
| CN1128256A (en) * | 1994-12-09 | 1996-08-07 | Basf公司 | Preparation of biuret-containing polyisocyanates |
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| US6414184B1 (en) * | 1996-08-19 | 2002-07-02 | Basf Aktiengesellschaft | Process for producing polyisocyanates containing biuret groups from (cyclo)aliphatic diisocyanates |
| CN102321231A (en) * | 2011-06-01 | 2012-01-18 | 甘肃银光聚银化工有限公司 | Method for preparing hexamethylene diisocyanate biuret curing agent |
| CN111217972A (en) * | 2020-01-13 | 2020-06-02 | 万华化学集团股份有限公司 | Preparation method of biuret polyisocyanate with storage stability |
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2022
- 2022-10-20 CN CN202211286198.5A patent/CN115894302A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE1101394B (en) * | 1958-04-24 | 1961-03-09 | Bayer Ag | Process for the production of polyisocyanates with a biuret structure |
| CN1128256A (en) * | 1994-12-09 | 1996-08-07 | Basf公司 | Preparation of biuret-containing polyisocyanates |
| US6414184B1 (en) * | 1996-08-19 | 2002-07-02 | Basf Aktiengesellschaft | Process for producing polyisocyanates containing biuret groups from (cyclo)aliphatic diisocyanates |
| CN1325935A (en) * | 2000-05-31 | 2001-12-12 | 西安诺亚环境科技有限公司 | Water preserving agent for cultivating forest on Chinese loess plateau |
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