CN113856751A - Catalyst, preparation method thereof and polymerization method of isocyanate - Google Patents
Catalyst, preparation method thereof and polymerization method of isocyanate Download PDFInfo
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- CN113856751A CN113856751A CN202111004543.7A CN202111004543A CN113856751A CN 113856751 A CN113856751 A CN 113856751A CN 202111004543 A CN202111004543 A CN 202111004543A CN 113856751 A CN113856751 A CN 113856751A
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- reaction
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- piperazine
- isocyanate
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- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 29
- 239000012948 isocyanate Substances 0.000 title claims abstract description 22
- 150000002513 isocyanates Chemical class 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 69
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000243 solution Substances 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 7
- GLUUGHFHXGJENI-UHFFFAOYSA-N diethylenediamine Natural products C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000004885 piperazines Chemical class 0.000 claims abstract description 6
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims abstract 3
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical class O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 125000002947 alkylene group Chemical class 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 238000006467 substitution reaction Methods 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 13
- 150000003384 small molecules Chemical class 0.000 abstract description 7
- 229920002521 macromolecule Polymers 0.000 abstract description 5
- 239000005056 polyisocyanate Substances 0.000 abstract description 2
- 229920001228 polyisocyanate Polymers 0.000 abstract description 2
- 238000002390 rotary evaporation Methods 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- 125000001453 quaternary ammonium group Chemical group 0.000 description 32
- 239000007795 chemical reaction product Substances 0.000 description 25
- 239000000178 monomer Substances 0.000 description 25
- 238000005160 1H NMR spectroscopy Methods 0.000 description 15
- 239000013638 trimer Substances 0.000 description 13
- 239000012295 chemical reaction liquid Substances 0.000 description 11
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 238000010790 dilution Methods 0.000 description 9
- 239000012895 dilution Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 239000006227 byproduct Substances 0.000 description 8
- 230000005311 nuclear magnetism Effects 0.000 description 8
- 238000004445 quantitative analysis Methods 0.000 description 8
- 238000004366 reverse phase liquid chromatography Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- -1 aliphatic isocyanates Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002574 poison Substances 0.000 description 4
- 231100000614 poison Toxicity 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- DDPRYTUJYNYJKV-UHFFFAOYSA-N 1,4-diethylpiperazine Chemical compound CCN1CCN(CC)CC1 DDPRYTUJYNYJKV-UHFFFAOYSA-N 0.000 description 2
- DFPJRUKWEPYFJT-UHFFFAOYSA-N 1,5-diisocyanatopentane Chemical compound O=C=NCCCCCN=C=O DFPJRUKWEPYFJT-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 150000002605 large molecules Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000005829 trimerization reaction Methods 0.000 description 2
- FDYWJVHETVDSRA-UHFFFAOYSA-N 1,1-diisocyanatobutane Chemical compound CCCC(N=C=O)N=C=O FDYWJVHETVDSRA-UHFFFAOYSA-N 0.000 description 1
- VKLNMSFSTCXMSB-UHFFFAOYSA-N 1,1-diisocyanatopentane Chemical compound CCCCC(N=C=O)N=C=O VKLNMSFSTCXMSB-UHFFFAOYSA-N 0.000 description 1
- VNMOIBZLSJDQEO-UHFFFAOYSA-N 1,10-diisocyanatodecane Chemical compound O=C=NCCCCCCCCCCN=C=O VNMOIBZLSJDQEO-UHFFFAOYSA-N 0.000 description 1
- GFNDFCFPJQPVQL-UHFFFAOYSA-N 1,12-diisocyanatododecane Chemical compound O=C=NCCCCCCCCCCCCN=C=O GFNDFCFPJQPVQL-UHFFFAOYSA-N 0.000 description 1
- ZGLYRKJNQPOLHW-UHFFFAOYSA-N 1,14-diisocyanatotetradecane Chemical compound O=C=NCCCCCCCCCCCCCCN=C=O ZGLYRKJNQPOLHW-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- QUPKOUOXSNGVLB-UHFFFAOYSA-N 1,8-diisocyanatooctane Chemical compound O=C=NCCCCCCCCN=C=O QUPKOUOXSNGVLB-UHFFFAOYSA-N 0.000 description 1
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 description 1
- WXVIZESSPOPCHK-UHFFFAOYSA-M 2-hydroxypropyl(trimethyl)azanium;octanoate Chemical compound CC(O)C[N+](C)(C)C.CCCCCCCC([O-])=O WXVIZESSPOPCHK-UHFFFAOYSA-M 0.000 description 1
- WJIOHMVWGVGWJW-UHFFFAOYSA-N 3-methyl-n-[4-[(3-methylpyrazole-1-carbonyl)amino]butyl]pyrazole-1-carboxamide Chemical compound N1=C(C)C=CN1C(=O)NCCCCNC(=O)N1N=C(C)C=C1 WJIOHMVWGVGWJW-UHFFFAOYSA-N 0.000 description 1
- KEZMBAQUUXDDDQ-UHFFFAOYSA-N CCC.N=C=O.N=C=O Chemical compound CCC.N=C=O.N=C=O KEZMBAQUUXDDDQ-UHFFFAOYSA-N 0.000 description 1
- KYIMHWNKQXQBDG-UHFFFAOYSA-N N=C=O.N=C=O.CCCCCC Chemical compound N=C=O.N=C=O.CCCCCC KYIMHWNKQXQBDG-UHFFFAOYSA-N 0.000 description 1
- OEMVAFGEQGKIOR-UHFFFAOYSA-N N=C=O.N=C=O.CCCCCCCC Chemical compound N=C=O.N=C=O.CCCCCCCC OEMVAFGEQGKIOR-UHFFFAOYSA-N 0.000 description 1
- FUCRTFHCJZBKBB-UHFFFAOYSA-N N=C=O.N=C=O.CCCCCCCCC Chemical compound N=C=O.N=C=O.CCCCCCCCC FUCRTFHCJZBKBB-UHFFFAOYSA-N 0.000 description 1
- DGOMVSNLFKNSAR-UHFFFAOYSA-N N=C=O.N=C=O.CCCCCCCCCC Chemical compound N=C=O.N=C=O.CCCCCCCCCC DGOMVSNLFKNSAR-UHFFFAOYSA-N 0.000 description 1
- DSSJCBOUEXFVFJ-UHFFFAOYSA-N N=C=O.N=C=O.CCCCCCCCCCC Chemical compound N=C=O.N=C=O.CCCCCCCCCCC DSSJCBOUEXFVFJ-UHFFFAOYSA-N 0.000 description 1
- SGXQOOUIOHVMEJ-UHFFFAOYSA-N N=C=O.N=C=O.CCCCCCCCCCCC Chemical compound N=C=O.N=C=O.CCCCCCCCCCCC SGXQOOUIOHVMEJ-UHFFFAOYSA-N 0.000 description 1
- PXDHKNWPVGTOCD-UHFFFAOYSA-N N=C=O.N=C=O.CCCCCCCCCCCCCC Chemical compound N=C=O.N=C=O.CCCCCCCCCCCCCC PXDHKNWPVGTOCD-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- STBLQDMGPBQTMI-UHFFFAOYSA-N heptane;isocyanic acid Chemical compound N=C=O.N=C=O.CCCCCCC STBLQDMGPBQTMI-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- ODYNBECIRXXOGG-UHFFFAOYSA-N n-butylbutan-1-amine;hydron;chloride Chemical compound [Cl-].CCCC[NH2+]CCCC ODYNBECIRXXOGG-UHFFFAOYSA-N 0.000 description 1
- NIXKBAZVOQAHGC-UHFFFAOYSA-M phenylmethanesulfonate Chemical compound [O-]S(=O)(=O)CC1=CC=CC=C1 NIXKBAZVOQAHGC-UHFFFAOYSA-M 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920000582 polyisocyanurate Polymers 0.000 description 1
- 239000011495 polyisocyanurate Substances 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/30—Only oxygen atoms
- C07D251/34—Cyanuric or isocyanuric esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
- C07D295/084—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
- C07D295/088—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明涉及多异氰酸酯聚合领域，具体涉及一种催化剂及其制备方法、异氰酸酯的聚合方法。所述催化剂为哌嗪类季铵碱类化合物，所述催化剂的制备方法步骤为：在Ar气氛保护下，将环氧丙烷滴加到哌嗪的脂肪族取代衍生物的水溶液中；在室温下搅拌，进行反应4‑9h；反应结束后取下层溶液，旋蒸得到哌嗪类季铵碱化合物，即所述催化剂。所述异氰酸酯聚合的方法为：在惰性气体的保护下，将异氰酸酯原料上述的催化剂的催化作用下进行聚合反应；当反应液中‑NCO含量基于反应液的重量达到5‑80wt％时，中止聚合反应。本发明在催化剂中引入环状哌嗪骨架，促进了小分子之间的反应，同时抑制大分子与小分子之间的反应，从而提高了底物的转化率并保证了产物的纯度。
The invention relates to the field of polyisocyanate polymerization, in particular to a catalyst and a preparation method thereof, and a polymerization method of isocyanate. The catalyst is a piperazine quaternary ammonium base compound, and the preparation method steps of the catalyst are: under the protection of Ar atmosphere, drop propylene oxide into the aqueous solution of the aliphatic substituted derivative of piperazine; Stir, and react for 4-9h; after the reaction, the lower layer solution is taken out, and the piperazine quaternary ammonium base compound is obtained by rotary evaporation, that is, the catalyst. The method for the isocyanate polymerization is as follows: under the protection of an inert gas, the polymerization reaction is carried out under the catalysis of the above-mentioned catalyst of the isocyanate raw material; when the NCO content in the reaction solution reaches 5-80wt% based on the weight of the reaction solution, the polymerization is terminated. reaction. The invention introduces a cyclic piperazine skeleton into the catalyst, which promotes the reaction between small molecules and simultaneously inhibits the reaction between macromolecules and small molecules, thereby improving the conversion rate of the substrate and ensuring the purity of the product.
Description
Technical Field
The invention relates to the field of polyisocyanate polymerization, and in particular relates to a catalyst, a preparation method thereof and a polymerization method of isocyanate.
Background
Diisocyanate polymers have unique advantages in various polyurethane coatings and adhesives and are widely used. However, monomers are volatile and toxic, and therefore, they are often prepared as multimers for use. Since the polyisocyanurate of aliphatic diisocyanate has excellent thermal stability, weather resistance and medium resistance, its self-polymerization reaction has been widely studied. The difficulty in the preparation process lies in the selection of the catalyst, and the types of the currently used catalysts are various and comprise: quaternary ammonium bases, quaternary ammonium salts, metal salts, hydrides, oxides, and the like. Therefore, how to prepare a novel catalyst by utilizing green and mild reaction conditions and ensure that the isocyanurate polymerization reaction catalyzed by the catalyst has higher monomer conversion rate and the trimer content in the product is a problem to be solved urgently.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the cyclic piperazine skeleton is introduced into the catalyst, so that the monomer conversion rate of the reaction is high, and the trimer in the product accounts for the main component.
The technical scheme adopted by the invention for solving the technical problems is as follows: in a first aspect, the catalyst has the general structural formula:
further, R in the structural general formula of the catalyst1Is an alkyl group having 1 to 20 carbon atoms.
Further, R in the structural general formula of the catalyst2Is hydroxyalkyl having 1 to 20 carbon atoms.
Further, the raw materials of the catalyst comprise aliphatic substituted derivatives of piperazine, water and alkylene oxide;
further, the aliphatic substituted derivatives of piperazine include 1, 4-dimethylpiperazine; the alkylene oxide comprises propylene oxide.
In a second aspect, a method of preparing the catalyst comprises: under the protection of Ar, dropwise adding a certain amount of propylene oxide into an aqueous solution of 1, 4-dimethylpiperazine, wherein the amount of water is 1.5-4 times of the molar amount of the 1, 4-dimethylpiperazine, and the amount of propylene oxide is 1.0-2.5 times of the molar amount of the 1, 4-dimethylpiperazine; then stirring at room temperature, and reacting for 4-9 h; taking the lower layer solution after the reaction is finished; and (4) performing rotary evaporation to obtain the piperazine quaternary ammonium base.
The main reaction equation is as follows:
in a third aspect, the isocyanate polymerization process comprises: under the protection of inert gas, taking isocyanate as a substrate and carrying out polymerization reaction under the catalysis of a catalyst, wherein the reaction temperature is 10-100 ℃ (preferably 30-80 ℃), and the dosage of the catalyst is 10-800ppm (preferably 200-800ppm) based on the mass of the substrate; the catalyst used in the present invention may be used in the form of a solution without a solvent or dissolved in a catalyst solvent, and when the catalyst is used in the form of a solution, the amount of the catalyst solution is 5 to 50 wt% (preferably 10 to 30 wt%) based on the amount of the reaction solution; when the-NCO content of the reaction liquid is 5 to 80 wt% (preferably 10 to 70 wt% or 20 to 50 wt%) based on the amount of the reaction liquid as the reaction proceeds, the reaction is terminated by a high-temperature treatment or by adding a catalyst poison in an amount of twice the molar amount or twice a slight excess amount of the catalyst.
Further, the catalyst solvent suitable for the present invention includes a straight or branched chain monohydric alcohol and dihydric alcohol having 1 to 20 carbon atoms, and includes one or more hydroxyl groups in the whole molecule; optional catalyst solvents include methanol, ethanol, 1-or 2-propanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-octanol, isooctanol, heptanol, 2-ethyl-1, 3-hexanediol, 1, 3-butanediol or 1, 4-butanediol, 1-methoxy-2-propanol, preferably methanol, n-butanol, hexanol, heptanol and isooctanol.
Further, suitable substrates for the present invention include all aliphatic isocyanates, wherein the substrate can be a single aliphatic isocyanate or a mixture of a plurality of aliphatic isocyanates; all structural or configurational isomers of the isocyanates listed below are optional examples: bis (isocyanatoalkyl) ethers, propane diisocyanate, butane diisocyanate, pentane diisocyanate (pentamethylene diisocyanate, PDI), hexane diisocyanate (hexamethylene diisocyanate, HDI), heptane diisocyanate, octane diisocyanate (e.g., octamethylene diisocyanate), nonane diisocyanate (e.g., trimethyl-HDI, TMDI, typically present as a mixture of the 2, 4, 4-and 2, 2, 4-isomers), triisocyanates (e.g., 4-isocyanatomethyl-1, 8-octane diisocyanate), decane diisocyanate (e.g., decamethylene diisocyanate) and triisocyanates, undecane diisocyanate and triisocyanates, dodecane diisocyanate (e.g., dodecamethylene diisocyanate) and triisocyanates, mixtures of these, and mixtures of these, Tetradecane diisocyanate (e.g., tetradecylene diisocyanate), 1, 4-cyclohexane diisocyanate (CHDI), 3-isocyanatomethyl-3, 5, 5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 4' -dicyclohexylmethane diisocyanate (H12MDI), and Pentamethylene Diisocyanate (PDI) is preferably used.
Further, catalyst poisons suitable for the present invention include acids or acid derivatives; alternative catalyst poisons include one or more of phosphoric acid, benzoyl chloride, phenylmethanesulfonate, phosphate esters, phosphite esters, methanesulfonic acid, p-toluenesulfonic acid and the like, with dibutyl phosphate being preferred.
The invention has the beneficial effects that:
according to the invention, a cyclic piperazine skeleton is introduced into a catalyst, so that the reaction among small molecules is promoted, the small molecule reaction comprises the dimerization reaction and the trimerization reaction of an isocyanate substrate, the reaction of an isocyanate substrate monomer and a small amount of alcohol in a system, and the reaction between a large molecule and the small molecule or the large molecule is inhibited, and the reaction of a generated polymer and the small amount of alcohol in the system and the polymerization reaction of the isocyanate substrate are inhibited, so that the purposes of high monomer conversion rate and the tripolymer in a product accounting for main components are achieved.
Drawings
The invention is further illustrated by the following figures and examples.
FIG. 1 is a GPC measurement result graph.
In the figure: a-a commercially available PDI trimer, B-a PDI trimer produced according to the present invention.
Detailed Description
The process provided by the present invention is further illustrated by the following examples, but the invention is not limited thereto. All percentages referred to in the present invention are mass percentages unless otherwise specified.
Example 1
The molar ratio of the 1, 4-dimethylpiperazine to the water to the propylene oxide is adjusted to 1:1.5: 1. Under Ar protection, propylene oxide (3.5ml) was added dropwise to 1, 4-dimethylpiperazine (6.8ml) and water (1.4ml) over 0.5 h. And then continuously stirring for 4 hours at room temperature to obtain a reaction product 1 #. And qualitatively analyzing the synthesized reaction product by adopting nuclear magnetism. The nuclear magnetic results are shown below:
monosubstituted quaternary ammonium bases1H NMR(400M，TMS):δ1.18(m，3H)，1.89(s，3H)，2.22-2.50(m，10H)，2.31(s，3H)，3.15-3.61(m，1H)，5.6(s，1H)。
Disubstituted quaternary ammonium bases1H NMR(400M，TMS):δ1.06(m，6H)，2.25-2.31(m，8H)，2.69(s，6H)，3.36-4.30(m，6H)，5.6(s，2H)。
Then, the reaction product is subjected to quantitative analysis by reverse phase liquid chromatography, and the result shows that: the mass content of the mono-substituted quaternary ammonium base is 35.1 percent, the mass content of the di-substituted quaternary ammonium base is 31.1 percent, and the mass content of the byproduct is 33.8 percent.
Example 2
The molar ratio of the 1, 4-dimethylpiperazine to the water to the propylene oxide is adjusted to 1:2: 1.4. Under Ar protection, propylene oxide (4.9ml) was added dropwise to 1, 4-dimethylpiperazine (6.8ml) and water (1.9ml) over 0.5 h. And then continuously stirring for 4 hours at room temperature to obtain a reaction product No. 2. And qualitatively analyzing the synthesized reaction product by adopting nuclear magnetism. The nuclear magnetic results are shown below:
monosubstituted quaternary ammonium bases1H NMR(400M，TMS):δ1.18(m，3H)，1.89(s，3H)，2.22-2.50(m，10H)，2.31(s，3H)，3.15-3.61(m，1H)，5.6(s，1H)。
Disubstituted quaternary ammonium bases1H NMR(400M，TMS):δ1.06(m，6H)，2.25-2.31(m，8H)，2.69(s，6H)，3.36-4.30(m，6H)，5.6(s，2H)。
Then, the reaction product is subjected to quantitative analysis by reverse phase liquid chromatography, and the result shows that: the mass content of the mono-substituted quaternary ammonium base is 19.1 percent, the mass content of the di-substituted quaternary ammonium base is 78.5 percent, and the mass content of a byproduct is 2.4 percent.
Example 3
The molar ratio of the 1, 4-dimethylpiperazine to the water to the propylene oxide is adjusted to 1:2: 1.4. Under Ar protection, propylene oxide (4.9ml) was added dropwise to 1, 4-dimethylpiperazine (6.8ml) and water (1.9ml) over 0.5 h. And then continuously stirring for 6 hours at room temperature to obtain a reaction product No. 3. And qualitatively analyzing the synthesized reaction product by adopting nuclear magnetism. The nuclear magnetic results are shown below:
monosubstituted quaternary ammonium bases1H NMR(400M，TMS):δ1.18(m，3H)，1.89(s，3H)，2.22-2.50(m，10H)，2.31(s，3H)，3.15-3.61(m，1H)，5.6(s，1H)。
Disubstituted quaternary ammonium bases1H NMR(400M，TMS):δ1.06(m，6H)，2.25-2.31(m，8H)，2.69(s，6H)，3.36-4.30(m，6H)，5.6(s，2H)。
Then, the reaction product is subjected to quantitative analysis by reverse phase liquid chromatography, and the result shows that: the mass content of the mono-substituted quaternary ammonium base is 7.7 percent, the mass content of the di-substituted quaternary ammonium base is 91.6 percent, and the mass content of the byproduct is 0.7 percent.
Example 4
The molar ratio of the 1, 4-dimethylpiperazine to the water to the propylene oxide is adjusted to 1:2: 1.4. Under Ar protection, propylene oxide (4.9ml) was added dropwise to 1, 4-dimethylpiperazine (6.8ml) and water (1.9ml) over 0.5 h. Then continuously stirring for 9h at room temperature to obtain a reaction product No. 4. And qualitatively analyzing the synthesized reaction product by adopting nuclear magnetism. The nuclear magnetic results are shown below:
monosubstituted quaternary ammonium bases1H NMR(400M，TMS):δ1.18(m，3H)，1.89(s，3H)，2.22-2.50(m，10H)，2.31(s，3H)，3.15-3.61(m，1H)，5.6(s，1H)。
Disubstituted quaternary ammonium bases1H NMR(400M，TMS):δ1.06(m，6H)，2.25-2.31(m，8H)，2.69(s，6H)，3.36-4.30(m，6H)，5.6(s，2H)。
Then, the reaction product is subjected to quantitative analysis by reverse phase liquid chromatography, and the result shows that: the mass content of the mono-substituted quaternary ammonium base is 9.2 percent, the mass content of the di-substituted quaternary ammonium base is 44.7 percent, and the mass content of the byproduct is 46.1 percent.
Example 5
The molar ratio of the 1, 4-dimethyl piperazine to the water to the propylene oxide is adjusted to be 1:2:2. Under Ar protection, propylene oxide (7.0ml) was added dropwise to 1, 4-dimethylpiperazine (6.8ml) and water (1.8ml) over 0.5 h. And then continuously stirring for 4 hours at room temperature to obtain a reaction product No. 5. And qualitatively analyzing the synthesized reaction product by adopting nuclear magnetism. The nuclear magnetic results are shown below:
monosubstituted quaternary ammonium bases1H NMR(400M，TMS):δ1.18(m，3H)，1.89(s，3H)，2.22-2.50(m，10H)，2.31(s，3H)，3.15-3.61(m，1H)，5.6(s，1H)。
Disubstituted quaternary ammonium bases1H NMR(400M，TMS):δ1.06(m，6H)，2.25-2.31(m，8H)，2.69(s，6H)，3.36-4.30(m，6H)，5.6(s，2H)。
Then, the reaction product is subjected to quantitative analysis by reverse phase liquid chromatography, and the result shows that: the mass content of the mono-substituted quaternary ammonium base is 19.6 percent, the mass content of the di-substituted quaternary ammonium base is 78.3 percent, and the mass content of a byproduct is 2.1 percent.
Example 6
The molar ratio of the 1, 4-dimethyl piperazine to the water to the propylene oxide is adjusted to be 1:2: 2.5. Under Ar protection, propylene oxide (8.8ml) was added dropwise over 0.5h to 1, 4-dimethylpiperazine (6.8ml) and water (0.1mol, 1.8 ml). And then continuously stirring for 4 hours at room temperature to obtain a reaction product No. 6. And qualitatively analyzing the synthesized reaction product by adopting nuclear magnetism. The nuclear magnetic results are shown below:
monosubstituted quaternary ammonium bases1H NMR(400M，TMS):δ1.18(m，3H)，1.89(s，3H)，2.22-2.50(m，10H)，2.31(s，3H)，3.15-3.61(m，1H)，5.6(s，1H)。
Disubstituted quaternary ammonium bases1H NMR(400M，TMS):δ1.06(m，6H)，2.25-2.31(m，8H)，2.69(s，6H)，3.36-4.30(m，6H)，5.6(s，2H)。
Then, the reaction product is subjected to quantitative analysis by reverse phase liquid chromatography, and the result shows that: the mass content of the mono-substituted quaternary ammonium base is 3.7 percent, the mass content of the di-substituted quaternary ammonium base is 93.4 percent, and the mass content of a byproduct is 2.9 percent.
Example 7
The molar ratio of 1, 4-diethylpiperazine, water and propylene oxide is adjusted to 1:2.5: 2.5. Under Ar protection, propylene oxide (8.8ml) was added dropwise over 0.5h to 1, 4-diethylpiperazine (6.8ml) and water (2.3 ml). And then continuously stirring for 4 hours at room temperature to obtain a reaction product No. 7. And qualitatively analyzing the synthesized reaction product by adopting nuclear magnetism. The nuclear magnetic results are shown below:
monosubstituted quaternary ammonium bases1H NMR(400M，TMS):δ1.18(m，3H)，1.89(s，3H)，2.22-2.50(m，10H)，2.31(s，3H)，3.15-3.61(m，1H)，5.6(s，1H)。
Disubstituted quaternary ammonium bases1H NMR(400M，TMS):δ1.06(m，6H)，2.25-2.31(m，8H)，2.69(s，6H)，3.36-4.30(m，6H)，5.6(s，2H)。
Then, the reaction product is subjected to quantitative analysis by reverse phase liquid chromatography, and the result shows that: the mass content of the mono-substituted quaternary ammonium base is 9.1 percent, the mass content of the di-substituted quaternary ammonium base is 88.6 percent, and the mass content of the byproduct is 2.3 percent.
Example 8
The molar ratio of the 1, 4-dimethylpiperazine to the water to the propylene oxide is adjusted to 1:4: 2.5. Under Ar protection, propylene oxide (8.8ml) was added dropwise to 1, 4-dimethylpiperazine (6.8ml) and water (3.6ml) over 0.5 h. And then continuously stirring for 4 hours at room temperature to obtain a reaction product 8 #. And qualitatively analyzing the synthesized reaction product by adopting nuclear magnetism. The nuclear magnetic results are shown below:
disubstituted quaternary ammonium bases1H NMR(400M，TMS):δ1.06(m，6H)，2.25-2.31(m，8H)，2.69(s，6H)，3.36-4.30(m，6H)，5.6(s，2H)。
Then, the reaction product is subjected to quantitative analysis by reverse phase liquid chromatography, and the result shows that: the mass content of the mono-substituted quaternary ammonium base is 0 percent, the mass content of the di-substituted quaternary ammonium base is 98.3 percent, and the mass content of a byproduct is 1.7 percent.
Trimers of PDI were prepared using the reaction products obtained in examples 1 to 8 above as catalysts, respectively, using PDI as a substrate, as shown in examples 9 to 12 below:
example 9
Weighing PDI (20g) monomer, adding the monomer into a reaction bottle, heating to 90 ℃ under the protection of Ar, preheating for one hour, controlling the temperature to be 80 ℃, dropwise adding 600ppm of uniformly mixed 1# catalyst solution (diluted by methanol with the dilution degree of 10%), controlling the dropwise adding speed to be 1 drop/15 s, and controlling the floating range of the reaction temperature to be not more than +/-1 ℃. When the-NCO value in the reaction liquid reaches about 40 wt%, dibutyl phosphate twice the molar amount of the initial catalyst is added immediately to terminate the reaction.
Example 10
Weighing PDI (20g) monomer, adding the monomer into a reaction bottle, heating to 90 ℃ under the protection of Ar, preheating for one hour, controlling the temperature to be 80 ℃, dropwise adding 600ppm of uniformly mixed 2# catalyst solution (diluted by methanol with the dilution degree of 10%), controlling the dropwise adding speed to be 1 drop/15 s, and controlling the floating range of the reaction temperature to be not more than +/-1 ℃. When the-NCO value in the reaction liquid reaches about 40 wt%, dibutyl phosphate twice the molar amount of the initial catalyst is added immediately to terminate the reaction.
Example 11
Weighing PDI (20g) monomer, adding the monomer into a reaction bottle, heating to 90 ℃ under the protection of Ar, preheating for one hour, controlling the temperature to be 80 ℃, dropwise adding 600ppm of uniformly mixed 3# catalyst solution (diluted by methanol with the dilution degree of 10%), controlling the dropwise adding speed to be 1 drop/15 s, and controlling the floating range of the reaction temperature to be not more than +/-1 ℃. When the-NCO value in the reaction liquid reaches about 40 wt%, dibutyl phosphate with twice molar weight of the initial catalyst is added immediately to terminate the reaction
Example 12
Weighing PDI (20g) monomer, adding the monomer into a reaction bottle, heating to 90 ℃ under the protection of Ar, preheating for one hour, controlling the temperature to be 80 ℃, dropwise adding 600ppm of uniformly mixed 4# catalyst solution (diluted by methanol with the dilution degree of 10%), controlling the dropwise adding speed to be 1 drop/15 s, and controlling the floating range of the reaction temperature to be not more than +/-1 ℃. When the-NCO value in the reaction liquid reaches about 40 wt%, dibutyl phosphate twice the molar amount of the initial catalyst is added immediately to terminate the reaction.
Example 13
Weighing PDI (20g) monomer, adding the monomer into a reaction bottle, heating to 90 ℃ under the protection of Ar, preheating for one hour, controlling the temperature to be 80 ℃, dropwise adding 600ppm of 5# catalyst solution which is uniformly mixed, (diluting with methanol, the dilution is 10%), the dropwise adding speed is 1 drop/15 s, and the floating range of the reaction temperature is controlled not to exceed +/-1 ℃. When the-NCO value in the reaction liquid reaches about 40 wt%, dibutyl phosphate twice the molar amount of the initial catalyst is added immediately to terminate the reaction.
Example 14
Weighing PDI (20g) monomer, adding the monomer into a reaction bottle, heating to 90 ℃ under the protection of Ar, preheating for one hour, controlling the temperature to be 80 ℃, dropwise adding 600ppm of uniformly mixed 6# catalyst solution (diluted by methanol with the dilution degree of 10%), controlling the dropwise adding speed to be 1 drop/15 s, and controlling the floating range of the reaction temperature to be not more than +/-1 ℃. When the-NCO value in the reaction liquid reaches about 40 wt%, dibutyl phosphate twice the molar amount of the initial catalyst is added immediately to terminate the reaction.
Example 15
Weighing PDI (20g) monomer, adding the monomer into a reaction bottle, heating to 90 ℃ under the protection of Ar, preheating for one hour, controlling the temperature to be 80 ℃, dropwise adding 600ppm of the uniformly mixed 7# catalyst solution (diluted by methanol with the dilution degree of 10%), controlling the dropwise adding speed to be 1 drop/15 s, and controlling the floating range of the reaction temperature to be not more than +/-1 ℃. When the-NCO value in the reaction liquid reaches about 40 wt%, dibutyl phosphate twice the molar amount of the initial catalyst is added immediately to terminate the reaction.
Example 16
Weighing PDI (20g) monomer, adding the monomer into a reaction bottle, heating to 90 ℃ under the protection of Ar, preheating for one hour, controlling the temperature to be 80 ℃, dropwise adding 600ppm of uniformly mixed 8# catalyst solution (diluted by methanol with the dilution degree of 10%), controlling the dropwise adding speed to be 1 drop/15 s, and controlling the floating range of the reaction temperature to be not more than +/-1 ℃. When the-NCO value in the reaction liquid reaches about 40 wt%, dibutyl phosphate twice the molar amount of the initial catalyst is added immediately to terminate the reaction.
Comparative example
Weighing PDI (20g) monomer, adding the monomer into a reaction bottle, heating to 90 ℃ under the protection of Ar, preheating for one hour, controlling the temperature to be stable at 80 ℃, dropwise adding 600ppm of uniformly mixed 2-hydroxypropyl trimethyl ammonium caprylate (9#) solution, (diluting with methanol, the dilution degree is 10%), the dropwise adding speed is 1 drop/15 s, and the floating range of the reaction temperature is controlled not to exceed +/-1 ℃. When the-NCO value in the reaction liquid reaches about 40 wt%, dibutyl phosphate twice the molar amount of the initial catalyst is added immediately to terminate the reaction.
The invention determines the-NCO content according to a hydrochloric acid-di-n-butylamine titration method. The invention tests the color number of the product according to the method of GB/T3143-1982. The present invention uses gel permeation chromatography (Agilent-1260, column Plgel MIXED-C, mobile phase tetrahydrofuran) to determine the polymer content. The reagents used in the synthesis of the catalysts of the present invention were purchased from aladdin and, if not specifically indicated, were all analytical grade. The amounts of 1, 4-dimethylpiperazine, water and propylene oxide used in examples 1 to 8 are shown in Table 1; the polymerization products obtained in examples 9 to 16 and comparative example were subjected to NCO content and color measurement, and the results are shown in Table 2.
TABLE 1 Experimental data Table for examples 1-8
TABLE 2 Experimental data Table for examples 9-16 and comparative examples
From tables 1, 2, examples 2-4 the catalysts were prepared using 1, 4-dimethylpiperazine to water and propylene oxide ratios for each of the 1:2:1.4, the reaction time is respectively 4, 6 and 9, the catalysts 2#, 3# and 4# prepared in the examples 2-4 are respectively used in the examples 9-11 to participate in PDI polymerization reaction, when the specific gravity of-NCO in the reaction solution reaches about 40 wt%, the content of the generated tripolymer is higher, and catalyst poison is added into the reaction system to quench the catalyst and terminate the polymerization reaction. The time for completing the polymerization reaction in examples 9-11 was 1h, 1.7h, and 1h, and the color numbers of the PDI trimers were 85, 40, and 90, respectively, and the above data indicate that when the catalyst was prepared in the same substrate ratio, the catalyst activity was higher at the preparation times of 4h and 9h, but the color number of the PDI trimer was higher, i.e., the PDI trimer was yellow, the product quality was lower, and the catalyst preparation time of 6h had a much higher quality than the catalysts preparation times of 4h and 9h, although the activity was lower.
The time taken for preparing the catalysts from table 1, table 2, example 2, and examples 5 to 6 was 4 hours and the specific gravities of 1, 4-dimethylpiperazine and water in the reaction solutions were also the same, the specific gravities of the propylene oxide in the reaction solutions were sequentially increased, and when the prepared catalysts 2#, 5#, and 6# were applied to PDI polymerization reactions, the time taken for completing the polymerization reactions in examples 9, 12, and 13 were 1 hour, 1.5 hours, and 4.2 hours, respectively, and the activity of the prepared catalysts was decreased as the ratio of propylene oxide in the reaction system of the catalyst preparation was increased. In example 7, the ratio of water in the reaction solution was increased to make 7# compared to example 6, and by applying 7# to example 14, the data showed that the time for completion of the polymerization reaction in example 14 was much less than 4.2 hours in example 13, and further showed that the increase of specific gravity of water in the reaction system during the preparation of the catalyst increased the activity of the catalyst.
By contrast, the catalyst 3# produced by the reaction under the conditions of example 3 has the best catalytic reaction effect when applied to the reaction of example 10; the time for completing the polymerization reaction in example 10 was 1.7h, and the color number was 40; the polymerization reaction in the comparative example was completed for 4 hours, and the color number was 40; compared with the comparative example, the time for completing the polymerization reaction of the example 10 is far shorter than that of the comparative example under the premise of ensuring the quality of the polymerization product. In addition, gel permeation chromatography experiments were also performed on the PDI trimer produced under the conditions of this example 10 and the PDI trimer on the market, as shown in fig. 1, in which the highest peak of the two curves is the peak of the PDI trimer, and the remaining peaks are the peaks of the multimer, and the areas of the peaks correspond to the content of the substance; from the GPC results, it can be seen that the trimer content in the present invention (69.1%) was similar to the commercial PDI trimer content (75.9%). In conclusion, the cyclic piperazine skeleton is introduced into the catalyst, so that the reaction between small molecules, such as dimerization and trimerization of the isocyanate substrate, and the reaction between the isocyanate substrate monomer and a small amount of alcohol in the system are promoted, and the reaction between macromolecules and the small molecules or the macromolecules, such as the reaction between the generated polymer and the small amount of alcohol in the system and the polymerization of the isocyanate substrate, are inhibited, so that the purposes of high monomer conversion rate and the tripolymer accounting for the main component are achieved.
In light of the foregoing description of preferred embodiments in accordance with the invention, it is to be understood that numerous changes and modifications may be made by those skilled in the art without departing from the scope of the invention. The technical scope of the present invention is not limited to the contents of the specification, and must be determined according to the scope of the claims.
Claims (10)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115246793A (en) * | 2022-07-28 | 2022-10-28 | 山东新和成精化科技有限公司 | Preparation method of diisocyanate trimer, catalyst and preparation method thereof |
| CN116082260A (en) * | 2023-02-10 | 2023-05-09 | 山东新和成精化科技有限公司 | Catalyst, preparation method thereof and preparation method of aliphatic isocyanate polymer |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1110858B (en) * | 1959-02-12 | 1961-07-13 | Bayer Ag | Process for the production of foams based on isocyanate |
| CN101056911A (en) * | 2004-11-18 | 2007-10-17 | 旭硝子株式会社 | Process for producing flexible polyurethane foam |
| CN101778877A (en) * | 2007-07-23 | 2010-07-14 | 陶氏环球技术公司 | Two part polyurethane curable composition having at use temperature scope substantially consistent g-modulus |
| CN105622462A (en) * | 2016-03-03 | 2016-06-01 | 万华化学集团股份有限公司 | Method for preparing biuret polyisocyanates |
| CN112939894A (en) * | 2021-02-05 | 2021-06-11 | 合肥工业大学 | Water phase preparation method of 1- (2-hydroxyethyl) -4- (2-hydroxypropyl) piperazine |
-
2021
- 2021-08-30 CN CN202111004543.7A patent/CN113856751A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1110858B (en) * | 1959-02-12 | 1961-07-13 | Bayer Ag | Process for the production of foams based on isocyanate |
| CN101056911A (en) * | 2004-11-18 | 2007-10-17 | 旭硝子株式会社 | Process for producing flexible polyurethane foam |
| CN101778877A (en) * | 2007-07-23 | 2010-07-14 | 陶氏环球技术公司 | Two part polyurethane curable composition having at use temperature scope substantially consistent g-modulus |
| CN105622462A (en) * | 2016-03-03 | 2016-06-01 | 万华化学集团股份有限公司 | Method for preparing biuret polyisocyanates |
| CN112939894A (en) * | 2021-02-05 | 2021-06-11 | 合肥工业大学 | Water phase preparation method of 1- (2-hydroxyethyl) -4- (2-hydroxypropyl) piperazine |
Non-Patent Citations (1)
| Title |
|---|
| 许昕彤等: "哌嗪季铵碱催化剂的合成及其在异氰酸酯聚合反应中的应用", 《化学学报》, vol. 79, pages 1113 - 1117 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115246793A (en) * | 2022-07-28 | 2022-10-28 | 山东新和成精化科技有限公司 | Preparation method of diisocyanate trimer, catalyst and preparation method thereof |
| CN116082260A (en) * | 2023-02-10 | 2023-05-09 | 山东新和成精化科技有限公司 | Catalyst, preparation method thereof and preparation method of aliphatic isocyanate polymer |
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