CN117887037A - Biuret polyisocyanate composition and preparation method thereof - Google Patents
Biuret polyisocyanate composition and preparation method thereof Download PDFInfo
- Publication number
- CN117887037A CN117887037A CN202211226660.2A CN202211226660A CN117887037A CN 117887037 A CN117887037 A CN 117887037A CN 202211226660 A CN202211226660 A CN 202211226660A CN 117887037 A CN117887037 A CN 117887037A
- Authority
- CN
- China
- Prior art keywords
- biuret
- diisocyanate
- peak areas
- absorption peaks
- sum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 239000005056 polyisocyanate Substances 0.000 title claims abstract description 52
- 229920001228 polyisocyanate Polymers 0.000 title claims abstract description 52
- 239000000203 mixture Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 59
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 46
- 238000010521 absorption reaction Methods 0.000 claims abstract description 37
- 239000004202 carbamide Substances 0.000 claims abstract description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000005227 gel permeation chromatography Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 42
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 37
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 35
- 239000003795 chemical substances by application Substances 0.000 claims description 29
- 239000011261 inert gas Substances 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000012295 chemical reaction liquid Substances 0.000 claims description 14
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 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 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 239000010409 thin film Substances 0.000 claims description 8
- 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 7
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 7
- 235000019253 formic acid Nutrition 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 235000019260 propionic acid Nutrition 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
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 claims description 2
- DFPJRUKWEPYFJT-UHFFFAOYSA-N 1,5-diisocyanatopentane Chemical compound O=C=NCCCCCN=C=O DFPJRUKWEPYFJT-UHFFFAOYSA-N 0.000 claims description 2
- QGLRLXLDMZCFBP-UHFFFAOYSA-N 1,6-diisocyanato-2,4,4-trimethylhexane Chemical compound O=C=NCC(C)CC(C)(C)CCN=C=O QGLRLXLDMZCFBP-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- JGCWKVKYRNXTMD-UHFFFAOYSA-N bicyclo[2.2.1]heptane;isocyanic acid Chemical compound N=C=O.N=C=O.C1CC2CCC1C2 JGCWKVKYRNXTMD-UHFFFAOYSA-N 0.000 claims description 2
- 150000001735 carboxylic acids Chemical group 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000003377 acid catalyst Substances 0.000 claims 1
- TWLCPLJMACDPFF-UHFFFAOYSA-N cyclohexane;1,2-diisocyanatoethane Chemical compound C1CCCCC1.O=C=NCCN=C=O TWLCPLJMACDPFF-UHFFFAOYSA-N 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 26
- 239000012948 isocyanate Substances 0.000 description 21
- 150000002513 isocyanates Chemical class 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 14
- 230000002572 peristaltic effect Effects 0.000 description 10
- -1 aromatic isocyanates Chemical class 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000004922 lacquer Substances 0.000 description 6
- 230000007774 longterm Effects 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000007256 debromination reaction Methods 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910002566 KAl(SO4)2·12H2O Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- ZOCMPVMKPVJTEP-UHFFFAOYSA-N diphepanol Chemical compound C=1C=CC=CC=1C(O)(C=1C=CC=CC=1)C(C)N1CCCCC1 ZOCMPVMKPVJTEP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000006223 plastic coating Substances 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/7806—Nitrogen containing -N-C=0 groups
- C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
- C08G18/7831—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing biuret groups
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a biuret polyisocyanate composition and a preparation method thereof, and the biuret polyisocyanate composition provided by the invention has excellent storage stability. The composition is derived from diisocyanate monomers; the ratio of the sum of the peak areas of the absorption peaks of the urea biuret A with the number average molecular weight below 1500 to the sum of the peak areas of the absorption peaks of the urea biuret B with the number average molecular weight below 1500 in the composition is 3.5-5:1, and the peak areas of the absorption peaks are measured by gel permeation chromatography; wherein the sum of peak areas of absorption peaks of the biuret A is an odd-numbered sum of peak areas of absorption peaks of the biuret with the number of structural units R in a molecular structure with a number average molecular weight below 1500; the sum of peak areas of absorption peaks of the biuret B is equal to or less than the sum of peak areas of absorption peaks of the biuret with even number of structural units R in a molecular structure with a number average molecular weight of 1500.
Description
Technical Field
The invention relates to a preparation technology of a biuret polyisocyanate composition, in particular to a biuret polyisocyanate composition and a preparation method thereof.
Background
The polyurethane paint is a polyurethane material with excellent performance synthesized by taking isocyanate and polyol as basic raw materials. The polyurethane coating has excellent performance and easy modification and adjustment due to the hard segment caused by isocyanate and the soft segment caused by polyol in the molecular chain, and is widely applied in the fields of automobile raw lacquer, automobile repair lacquer, plastic coating, anticorrosive coating, wood lacquer, industrial lacquer and the like due to the excellent mechanical wear resistance, good flexibility, strong adhesive force, excellent chemical resistance and the like.
The industrial isocyanate product used in polyurethane paint mainly comprises MDI, NDI, TDI, PDI, HDI, IPDI, H 12 MDI and XDI, etc., are classified into aromatic isocyanates and aliphatic (cyclo) isocyanates. The downstream product of the aliphatic (cyclo) isocyanate curing agent has good yellowing resistance, so that the aliphatic (cyclo) isocyanate curing agent has wider application in high-end fields such as automotive raw lacquer, automotive refinish lacquer and the like, and particularly the isocyanate curing agent product with HDI as a matrix is mainly used. The isocyanate curing agent based on HDI in the market is mainly two products of HDI trimer and HDI biuret, wherein the curing agent based on HDI biuret is known to have excellent flexibility and strong adhesive force of coating film, and is widely appliedIs used in the field of industrial paint and heavy corrosion protection.
For biuret isocyanate curing agents, such as HDI biuret curing agents, which are mainly used in high-end fields, downstream customers have higher requirements on color number and free HDI monomer content. The initial color number and free HDI monomer content of a biuret isocyanate curing agent (e.g., an HDI biuret curing agent) can be made low, but both gradually rise during long-term storage, so improving the stability of color number and free isocyanate monomer (e.g., free HDI monomer) content during storage of a biuret isocyanate curing agent (e.g., an HDI biuret curing agent) is an important study by those skilled in the art.
Chinese patent application CN114316210a discloses a process for the preparation of biuret polyisocyanates by controlling the content of 0.003-0.1wt% of hindered phenol antioxidant in the combined state in the biuret polyisocyanate composition to achieve a stable color number maintenance of the biuret polyisocyanate composition during long-term storage, but no mention is made of free HDI monomer stability during storage of the biuret polyisocyanate composition.
Chinese patent CN105601565B discloses a process for preparing biuret polyisocyanate composition by reacting polyisocyanate with water in the presence of substituted 8-aminomethylquinoline compound and hydrazine derivative, the color number of the prepared product is less than 20Hazen, the monomer increment for 6 months of storage of the product is less than 0.1wt%, the long-term storage stability of the prepared biuret polyisocyanate product is good, the process does not mention the color number stability of the biuret polyisocyanate composition during storage.
Chinese patent application CN110982045A discloses an isocyanate curing agent with low viscosity and low color number and a preparation method thereof, long-chain alcohol is used as a modified raw material, the peroxide content in the long-chain alcohol is controlled to be less than or equal to 500ppm, isocyanate, the long-chain alcohol and a catalyst are mixed for reaction, the polarity of polyisocyanate can be effectively reduced by using the long-chain alcohol, so that the viscosity of the curing agent is reduced, and in addition, some long-chain fatty alcohols used play a role of a surfactant to a certain extent, so that the tolerance of dimethylbenzene is improved. In addition, the patent document can prepare isocyanate curing agent with low viscosity and low color number by controlling the content of peroxide and double bond in long-chain alcohol, which is beneficial to improving the storage stability of the curing agent. This patent document promotes color number stability of the isocyanate curing agent during storage by means of alcohol modification, however, it is well known to those skilled in the art that the modification means may alter the structure of the isocyanate itself, thereby affecting the downstream application properties of the isocyanate curing agent.
Chinese patent application CN111635502a discloses a method for preparing a polyisocyanate composition, which relates to reacting isocyanate with binary to quaternary organic polyhydroxy compound to obtain a prepolymer reaction solution, the prepolymer reaction solution is subjected to debromination treatment by using a special debromination agent, and then separation and purification are performed to obtain the polyisocyanate composition, the polyisocyanate composition is stored at room temperature for at least 12 months to keep stable color number, and the preparation process of the debromination agent is complex and is not beneficial to industrial implementation.
Chinese patent application CN112225857a discloses an isocyanurate-containing polyisocyanate composition with stable color number and a preparation method thereof, in which an isocyanate monomer is used to perform polymerization reaction in the presence of a catalyst, a prepolymer is obtained after termination reaction, and after separation treatment and heat treatment, the isocyanurate-containing polyisocyanate composition is obtained.
It can be seen that the conventional art has mostly increased the stability of the free diisocyanate monomer of the biuret polyisocyanate curing agent or the color number stability during storage by adding additional auxiliaries, but the addition of additives adds additional cost and affects the performance properties thereof.
Disclosure of Invention
In view of the above, the present invention provides a biuret polyisocyanate composition having excellent storage stability, a small increase in color number of the biuret polyisocyanate composition after long-term storage, and a small increase in content of free diisocyanate monomers, and a method for producing the same.
The invention provides the following technical scheme for achieving the purpose:
the present invention provides a biuret polyisocyanate composition derived from diisocyanate monomers selected from one or more of aliphatic diisocyanates, cycloaliphatic diisocyanates; the ratio of the sum of peak areas of absorption peaks of the urea biuret a having a number average molecular weight of 1500 or less to the sum of peak areas of absorption peaks of the urea biuret B having a number average molecular weight of 1500 or less (hereinafter or simply referred to as "parity ratio") in the composition, which peak areas are measured by gel permeation chromatography using a differential refractive index detector, is 3.5 to 5:1;
wherein the sum of peak areas of absorption peaks of the biuret A is an odd-numbered sum of peak areas of absorption peaks of the biuret with the number of structural units R in a molecular structure with a number average molecular weight below 1500;
the sum of peak areas of absorption peaks of the biuret B is equal to or less than the sum of peak areas of absorption peaks of the biuret with even number of structural units R in a molecular structure with a number average molecular weight of 1500;
the structural unit R is a part except NCO groups of the diisocyanate monomer.
Specifically, the biuret A is a biuret obtained by reacting an odd number of diisocyanate monomers with a biuretizing agent, and the molecular structure of the biuret A contains an odd number of structural units R; the biuret B is a biuret obtained by reacting an even number of diisocyanate monomers with a biuretizing agent, and the molecular structure of the biuret B contains an even number of structural units R.
Preferably, the number of structural units R in the molecular structure of said biuret A is an odd number from 3 to 9, such as tribiuret, pentabiuret, heptabiuret and nonabiuret; the number of structural units R in the molecular structure of the biuret B is an even number in the range from 2 to 8, such as biuret, tetrabiuret, hexabiuret and octabiuret. In the molecular structure of the biuret A or the biuret B, the biuret compound containing N structural units R is called N biuret, for example, the biuret compound containing three structural units R is tribiuret, tetrabiuret, pentabiuret or the like.
In some embodiments, the sum of peak areas of absorption peaks of the biuret a in the composition is the sum of peak areas of absorption peaks of the biuret having a number average molecular weight of less than 1500 for the number of structural units R of 3, 5, 7, 9; the sum of peak areas of absorption peaks of the biuret B is the sum of peak areas of absorption peaks of the biuret with the number of structural units R in the molecular structure with the number average molecular weight of less than 1500 being 2, 4, 6 and 8.
The present inventors have found that the storage stability of the composition can be significantly improved by controlling the ratio of the sum of the peak areas of the absorption peaks of the biuret A having a number average molecular weight of 1500 or less to the sum of the peak areas of the absorption peaks of the biuret B having a number average molecular weight of 1500 or less in the composition to 3.5 to 5:1.
In some embodiments, the diisocyanate monomer is selected from one or more of pentamethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, 1, 4-cyclohexane diisocyanate, methylcyclohexyl diisocyanate, norbornane diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate, lysine diisocyanate, cyclohexanedimethylene diisocyanate, preferably one or more of hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, more preferably hexamethylene diisocyanate.
The present invention also provides a process for the preparation of a biuret polyisocyanate composition as described above comprising the steps of:
1) Performing heat treatment on diisocyanate monomers at 90-110 ℃ under the condition of introducing inert gas to obtain a reaction liquid after heat treatment, and then heating the reaction liquid after heat treatment; preferably, in step 1), the time of the heat treatment is 30min-50min; the gas velocity U of the inert gas in step 1) and the molar amount (i.e., amount of substance) W of the diisocyanate monomer added in step 1) satisfy the following relationship: 500-500 (U.500)/W is less than or equal to 1000, and U is L/h;
2) Stopping introducing the inert gas after the temperature of the reaction liquid is raised to 120-150 ℃ after the heat treatment, and then introducing a biuretizing reagent for polymerization reaction until the conversion rate reaches 10-80%, preferably 30-60%;
3) Then the inert gas is introduced again, the reaction liquid is subjected to heat treatment at 120-150 ℃, and residual diisocyanate monomers are removed to obtain a product; preferably, in the step 3), the time of the heat treatment is 30min-50min; in step 3), the gas velocity V of the inert gas and the molar amount W of the diisocyanate monomer added in step 1) satisfy the following relationship: 150.ltoreq.V.times.500)/W.ltoreq.600, V being in units of L/h.
According to the preparation method, the composition with excellent storage stability can be prepared by reacting through a specific heating reaction program and an inert gas inlet program.
The inventors have found that O in the reaction system can be removed by introducing an inert gas at the initial stage of the reaction and performing the pre-reaction at 90 to 110 DEG C 2 Reducing the side reaction of diisocyanate monomer in the reaction kettle to generate a chromogenic substance in a high-temperature environment. According to the invention, inert gas is introduced at the initial stage of the reaction and pre-reaction is carried out at 90-110 ℃, then the temperature is raised to 120-150 ℃ to continue the reaction to the target conversion rate, finally, inert gas is introduced again at 120-150 ℃ to continue the reaction for a period of time, and the speed of the inert gas is controlled according to a specific mode in the process of introducing the inert gas, so that the composition with the ratio of the peak area of the absorption peak of the urea acetal with the number average molecular weight below 1500 to the urea acetal with the number average molecular weight below 1500 of 3.5-5:1 can be obtained, and the product with obviously improved storage stability is obtained. The adoption of the specific process program of the invention can reduce the generation of trace chromogenic groups and reduce the trace O possibly existing in a reaction system 2 The possibility of generating a chromogenic substance by side reaction of diisocyanate monomers in the reaction kettle in a high-temperature environment is reduced, and the product can be effectively improvedThe storage stability effectively improves the problem that the color number of the biuret polyisocyanate curing agent is gradually increased in the long-period storage process, thereby reducing the influence on downstream application.
In the step 1), the gas speed U of the inert gas and the molar quantity W of the diisocyanate monomer added in the step 1) satisfy the following relation: 500-500 (U-500)/W-1000; preferably, the following relation is satisfied: 600-500 (U)/W-800; wherein U is L/h; the gas velocity U of the inert gas in the step 1) is controlled in the preferred mode, so that the storage stability of the product is further improved.
In a preferred embodiment, in step 1), the diisocyanate monomer is added into the reaction vessel in advance, and the addition amount of the diisocyanate monomer is 20 to 90%, preferably 40 to 70% of the volume of the reaction vessel.
In the step 3), the gas velocity V of the inert gas and the molar quantity W of the diisocyanate monomer added in the step 1) satisfy the following relation: 150-500V/W-600; preferably, the following relation is satisfied: the ratio of V to W is less than or equal to 300 and less than or equal to 500; wherein, the unit of V is L/h, and the gas speed V of the inert gas in the step 3) is controlled by adopting the optimized mode, thereby being beneficial to further improving the storage stability of the product.
In some embodiments, in step 2), the biuretizing agent is selected from one or more of water, crystalline hydrate, preferably water. Wherein the crystalline hydrate may be various crystalline hydrates conventionally used in the art, such as but not limited to Na 2 SO 4 ·10H 2 O，CuSO 4 ·5H 2 O，KAl(SO 4 ) 2 ·12H 2 O，FeSO4·7H 2 O，Na 2 CO 3 ·10H 2 O，ZnSO 4 ·7H 2 O，MgSO4·7H 2 O, etc.
In some embodiments, the molar ratio of the biuretizing agent added in step 2) to the diisocyanate monomer added in step 1) is from 1:2 to 30, preferably from 1:4 to 15.
In some embodiments, the inert gas is nitrogen;
in some embodiments, in step 3), the residual diisocyanate monomer is removed by thin film evaporation;
in some embodiments, in step 2), the polymerization reaction is performed in the presence of a catalyst, which is a carboxylic acid type catalyst; preferably, the catalyst is selected from one or more of formic acid, acetic acid, propionic acid, pivalic acid, oxalic acid and malonic acid; preferably, the catalyst is used in an amount of 0.01 to 5wt%, more preferably 0.02 to 2wt%, based on the mass of the diisocyanate monomer added in step 1).
The inventors have long studied and found that the rise in free diisocyanate monomer content and increase in color number of a biuret polyisocyanate composition (e.g., an HDI biuret polyisocyanate composition) during long-period storage has a close relationship with degradation and polymerization of its biuret molecules. Taking HDI as an example, compared with the six-membered ring of the HDI trimer, the stability of the linear covalent bond between HDI in the HDI biuret molecule is poor, so that the problem that the content of free HDI monomer is gradually increased due to the degradation of the biuret molecule can occur when the HDI biuret curing agent is stored for a long period, and the HDI monomer has strong volatility and high toxicity, and the excessive free HDI monomer causes adverse effects on personnel health and environment when the HDI biuret curing agent is constructed at the downstream. At the same time, there is a tendency for the biuret molecules to polymerize, resulting in an increase in the color number of the product. The inventors of the present invention have surprisingly found, after long-term intensive studies, that in a biuret polyisocyanate composition, the ratio of peak areas of absorption peaks of a biuret a and a biuret B having a molecular weight of 1500 or less is 3.5 to 5:1 in a measurement spectrum of the composition obtained by gel permeation chromatography, so that the relative stability of the product components can be achieved, the degradation and polymerization of the biuret can be reduced, the generation of free diisocyanate monomers can be effectively reduced, and the color number deepening caused by the polymerization of the biuret can be avoided.
The technical scheme provided by the invention has the following beneficial effects:
the present invention can significantly improve the storage stability of a composition by controlling the ratio of the sum of the peak areas of the absorption peaks of a biuret A (the number of structural units R is an odd number) having a number average molecular weight of 1500 or less to the sum of the peak areas of the absorption peaks of a biuret B (the number of structural units R is an even number) having a number average molecular weight of 1500 or less in a biuret polyisocyanate composition within a specific range. The biuret polyisocyanate composition provided by the invention can be prepared by adopting the preparation method provided by the invention, and the composition prepared by adopting the preparation method provided by the invention has excellent storage stability, and can realize that the product color number rise evaluated by platinum-cobalt color number after being stored for 12 months at 25 ℃ is less than or equal to 5Hazen, and the free diisocyanate monomer content rise is less than or equal to 0.1%.
Detailed Description
In order that the invention may be readily understood, a further description of the invention will be provided with reference to the following examples. It should be understood that the following examples are only for better understanding of the present invention and are not meant to limit the present invention to the following examples.
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 term "and/or" as may be used herein includes any and all combinations of one or more of the associated listed items.
Where specific experimental steps or conditions are not noted in the examples, they may be performed according to the operations or conditions of the corresponding conventional experimental steps in the art. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention. The terms "first," "second," and the like, as referred to or possible in this specification, are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
Main raw material information:
hexamethylene diisocyanate, wannate HDI, wanhua chemistry, purity 99.5%,
isophorone diisocyanate, wannate IPDI, wanhua chemistry, purity 99.5%,
dicyclohexylmethane diisocyanate, wannate HMDI, wanhua chemistry, purity 99.5%,
formic acid, sigma-Aldrich, purity 98%,
acetic acid, sigma-Aldrich, purity 99%,
propionic acid, sigma-Aldrich, purity 99.5%,
pivalic acid, sigma-Aldrich, purity 99%.
In the following examples or comparative examples, the ratio of the sum of peak areas of absorption peaks of the urea biuret A having a number average molecular weight of 1500 or less to the sum of peak areas of absorption peaks of the urea biuret B having a number average molecular weight of 1500 or less (hereinafter, simply referred to as "parity ratio") was measured in the following manner:
GPC (gel permeation chromatography) was performed on the biuret polyisocyanate composition under the measurement conditions shown below, and then the peak areas of the absorption peaks of tribiuret, pentabiuret, heptabiuret and nonabiuret in the obtained spectra were added to be C, the peak areas of the absorption peaks of biuret, tetrabiuret, hexabiuret and octabiuret were added to be D, and the ratio C/D was calculated from the obtained C and D, i.e., the parity biuret ratio having a number average molecular weight of 1500 or less.
Measurement conditions:
instrument: agilent 1260 Infinicity II GPC/SEC gel chromatograph systems,
chromatographic column: MZ-Gel SDplus10E3A 5 μm,
a detector: a differential refractive light detector is shown and,
column oven and detector temperature: 35 c,
mobile phase: tetrahydrofuran (Sigma-Aldrich, HPLC, purity 99.9%),
mobile phase flow rate: 1.0mL/min of the total weight of the mixture,
analysis duration: and 40min.
The colour number of the biuret polyisocyanate composition product was determined by GB/T3143-1982 for its platinum cobalt colour number, in particular using an LCS IV liquid colour difference meter from Pick, germany.
The detection of the free diisocyanate monomer content adopts the national standard GB/T1846-2009.
Example 1
Step 1): 1605g Hexamethylene Diisocyanate (HDI) was added to a 5L stainless steel reactor via peristaltic pump, nitrogen was introduced at a rate of 9.6L/h, the temperature was raised and stirring was turned on, and the temperature was maintained for 30min when it was raised to 90 ℃; then heating;
step 2): when the temperature is raised to 120 ℃, stopping introducing nitrogen; 0.2g of formic acid is added through a peristaltic pump, and 80g of water is added through a water vapor generator; the reaction is carried out until the conversion rate reaches 25 percent, and the temperature of a reaction system is kept at 120 ℃;
step 3): then nitrogen is again introduced at the temperature of 120 ℃ at the rate of 2.9L/h, and the reaction is ended after 30min;
and removing monomers from the reaction liquid obtained by the reaction through a thin film evaporator to obtain a biuret polyisocyanate product.
Examples 2 to 8
The biuret polyisocyanate product was prepared with reference to the preparation method in example 1, except that: the biuret polyisocyanates of the examples were prepared with reference to the different operating conditions of the examples shown in Table 1.
TABLE 1 operating control conditions for examples 1-8
Comparative example 1 (compared to example 1)
Under the nitrogen atmosphere (the nitrogen introducing rate is not regulated in the reaction process), 1605g of Hexamethylene Diisocyanate (HDI) is added into a 5L stainless steel reaction kettle through a peristaltic pump, the temperature is raised, stirring is started, 0.2g of formic acid is added through the peristaltic pump when the temperature is raised to 120 ℃, 80g of water is added through a steam generator, and the reaction is finished after the conversion rate is controlled to 25%;
and removing the monomer from the obtained biuret reaction liquid through a thin film evaporator to obtain a biuret polyisocyanate product.
Comparative example 2 (compared to example 2)
Under the nitrogen atmosphere (the nitrogen introducing rate is not regulated in the reaction process), 1590g of isophorone diisocyanate (IPDI) is added into a 5L stainless steel reaction kettle through a peristaltic pump, the temperature is raised, stirring is started, 0.3g of formic acid is added through the peristaltic pump when the temperature is raised to 120 ℃, 43.0g of water is added through a steam generator, and the reaction is finished after the conversion rate is controlled to 25%;
and removing the monomer from the obtained biuret reaction liquid through a thin film evaporator to obtain a biuret polyisocyanate product.
Comparative example 3 (compared to example 3)
Under the nitrogen atmosphere (the nitrogen introducing rate is not regulated in the reaction process), 1605g of dicyclohexylmethane diisocyanate (HMDI) is added into a 5L stainless steel reaction kettle through a peristaltic pump, the temperature is raised, stirring is started, 0.3g of formic acid is added through the peristaltic pump when the temperature is raised to 120 ℃, 36.8g of water is added through a steam generator, and the reaction is finished after the conversion rate is controlled to 25%;
and removing the monomer from the obtained biuret reaction liquid through a thin film evaporator to obtain a biuret polyisocyanate product.
Comparative example 4 (compared to example 8)
Under the nitrogen atmosphere (the nitrogen introducing rate is not regulated in the reaction process), 4280g of Hexamethylene Diisocyanate (HDI) is added into a 5L stainless steel reaction kettle through a peristaltic pump, the temperature is raised, stirring is started, 213g of pivalic acid is added through the peristaltic pump when the temperature is raised to 150 ℃, 15.8g of water is added through a steam generator, and the reaction is finished after the conversion rate is controlled to 80%;
and removing the monomer from the obtained biuret reaction liquid through a thin film evaporator to obtain a biuret polyisocyanate product.
Comparative examples 5 to 8
The biuret polyisocyanate product was prepared with reference to the preparation method in example 1, except that: the biuret polyisocyanates of each comparative example were prepared with reference to the different operating conditions of each comparative example shown in Table 2.
TABLE 2 control conditions for comparative examples 5-8
And removing the monomer from the obtained biuret reaction liquid through a thin film evaporator to obtain a biuret polyisocyanate product.
The initial color number, free diisocyanate monomer content, and parity urea ratio of less than 1500 number average molecular weight of the biuret polyisocyanate products obtained in examples 1-8 and comparative examples 1-8 are shown in Table 3; the biuret polyisocyanate products obtained in each example and comparative example were stored at 25℃for 12 months, and the color number and the free diisocyanate monomer content of the products were retested, and the data are shown in Table 3:
TABLE 3 products of examples 1-8 and comparative examples 1-8
From the results of examples 1 to 8 and comparative examples 1 to 8, it is understood that the produced biuret polyisocyanates have a number average molecular weight of less than 1500 and a parity ratio of 3.5 to 5, have better storage stability than the higher or lower parity ratio products.
As can be seen from the experimental results of examples 1-8 of the present application, biuret polyisocyanates having a number average molecular weight below 1500 and a parity of 3.5-5 can be produced using the process scheme of the present invention, which products after storage at 25℃for 12 months have a color number increase of less than 5Hazen and a free diisocyanate monomer content increase of less than 0.1%. In comparative examples 1 to 8, which do not use the biuret polyisocyanates prepared according to the process scheme of the present invention, the parity ratio of the number average molecular weight below 1500 is < 3.5 or > 5, and the color number increases above 5Hazen after storage at 25℃for 12 months, and the free diisocyanate monomer content increases above 0.1%.
It will be readily appreciated that the above embodiments are merely examples given for clarity of illustration and are not meant to limit the invention thereto. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (10)
1. A biuret polyisocyanate composition, characterized in that the composition is derived from diisocyanate monomers selected from one or more of aliphatic diisocyanates, cycloaliphatic diisocyanates; the ratio of the sum of the peak areas of the absorption peaks of the urea biuret A with the number average molecular weight below 1500 to the sum of the peak areas of the absorption peaks of the urea biuret B with the number average molecular weight below 1500 in the composition is 3.5-5:1, and the peak areas of the absorption peaks are measured by gel permeation chromatography using a differential refractive index detector;
wherein the sum of peak areas of absorption peaks of the biuret A is an odd-numbered sum of peak areas of absorption peaks of the biuret with the number of structural units R in a molecular structure with a number average molecular weight below 1500;
the sum of peak areas of absorption peaks of the biuret B is equal to or less than the sum of peak areas of absorption peaks of the biuret with even number of structural units R in a molecular structure with a number average molecular weight of 1500;
the structural unit R is a part except NCO groups of the diisocyanate monomer.
2. The biuret polyisocyanate composition of claim 1, wherein the odd number is an odd number of 3-9; the even number is an even number in 2-8;
preferably, the sum of peak areas of absorption peaks of the biuret A is equal to or less than 3, 5, 7, 9 in number of structural units R in a molecular structure with a number average molecular weight of 1500; the sum of peak areas of absorption peaks of the biuret B is the sum of peak areas of absorption peaks of the biuret with the number of structural units R in a molecular structure with a number average molecular weight of less than 1500 being 2, 4, 6 and 8.
3. The biuret polyisocyanate composition of claim 1 or 2, wherein the diisocyanate monomer is selected from one or more of pentamethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, 1, 4-cyclohexane diisocyanate, methylcyclohexyl diisocyanate, norbornane diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate, lysine diisocyanate, cyclohexane dimethylene diisocyanate, preferably one or more of hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, more preferably hexamethylene diisocyanate.
4. A process for the preparation of a biuret polyisocyanate composition as claimed in any one of claims 1 to 3, comprising the steps of:
1) Performing heat treatment on diisocyanate monomers at 90-110 ℃ under the condition of introducing inert gas to obtain a reaction liquid after heat treatment, and then heating the reaction liquid after heat treatment; preferably, in step 1), the time of the heat treatment is 30min-50min; the gas velocity U of the inert gas in the step 1) and the molar amount W of the diisocyanate monomer added in the step 1) satisfy the following relation: 500-500 (U.500)/W is less than or equal to 1000, and U is L/h;
2) Stopping introducing the inert gas after the temperature of the reaction liquid is raised to 120-150 ℃ after the heat treatment, and then introducing a biuretizing reagent for polymerization reaction until the conversion rate reaches 10-80%, preferably 30-60%;
3) Then the inert gas is introduced again, the reaction liquid is subjected to heat treatment at 120-150 ℃, and residual diisocyanate monomers are removed to obtain a product; preferably, in the step 3), the time of the heat treatment is 30min-50min; in step 3), the gas velocity V of the inert gas and the molar amount W of the diisocyanate monomer added in step 1) satisfy the following relationship: 150.ltoreq.V.times.500)/W.ltoreq.600, V being in units of L/h.
5. The process according to claim 4, wherein in step 1), the gas velocity U of the inert gas and the molar amount W of the diisocyanate monomer added in step 1) satisfy the following relationship:
600≤(U*500)/W≤800。
6. the preparation method according to claim 4 or 5, wherein in step 1), the diisocyanate monomer is previously added to the reaction vessel, and the addition amount of the diisocyanate monomer is 20 to 90%, preferably 40 to 70% of the volume of the reaction vessel.
7. The process according to any one of claims 4 to 6, wherein in step 3), the gas velocity V of the inert gas and the molar amount W of the diisocyanate monomer added in step 1) satisfy the following relationship:
300≤(V*500)/W≤500。
8. the method according to any one of claims 4 to 6, wherein in step 2) the biuretizing agent is selected from one or more of water, crystalline hydrate, preferably water.
9. The process according to any one of claims 4 to 8, characterized in that the molar ratio of the biuretizing agent added in step 2) to the diisocyanate monomer added in step 1) is from 1:2 to 30, preferably from 1:4 to 15.
10. The production method according to any one of claims 4 to 7, wherein the inert gas is nitrogen;
and/or, in step 3), the residual diisocyanate monomer is removed by means of thin film evaporation;
and/or, in the step 2), the polymerization reaction is carried out in the presence of a catalyst, wherein the catalyst is a carboxylic acid catalyst; preferably, the catalyst is selected from one or more of formic acid, acetic acid, propionic acid, pivalic acid, oxalic acid and malonic acid; preferably, the catalyst is used in an amount of 0.01 to 5wt%, more preferably 0.02 to 2wt%, based on the mass of the diisocyanate monomer added in step 1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211226660.2A CN117887037A (en) | 2022-10-09 | 2022-10-09 | Biuret polyisocyanate composition and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211226660.2A CN117887037A (en) | 2022-10-09 | 2022-10-09 | Biuret polyisocyanate composition and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117887037A true CN117887037A (en) | 2024-04-16 |
Family
ID=90649405
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211226660.2A Pending CN117887037A (en) | 2022-10-09 | 2022-10-09 | Biuret polyisocyanate composition and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117887037A (en) |
-
2022
- 2022-10-09 CN CN202211226660.2A patent/CN117887037A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1923413B1 (en) | Coating agent | |
| EP1731582B1 (en) | Coating agent comprising oligocarbonate for scratch-resistant finishing lacquer | |
| JP7412563B2 (en) | Storage-stable polyisocyanate compositions and methods of preparation | |
| CN101205290B (en) | Isocyanate modified epoxy acrylic ester and preparation thereof | |
| CN107304244B (en) | Modified polyisocyanate composition and preparation method thereof | |
| CN102516465A (en) | High-elasticity waterborne polyurethane-acrylate composite resin, and preparation method and application thereof | |
| CN110183390B (en) | Preparation method of bio-based pentamethylene diisocyanate trimer | |
| KR20080045233A (en) | Polyisocyanate composition and coating composition containing the same | |
| JPH11152321A (en) | Urethane prepolymer, its production, and coating composition using it | |
| JP2001026626A (en) | Light-fast polyisocyanate having high solubility to nonpolar solvent | |
| EP1923414A2 (en) | Coating agent | |
| US20180355211A1 (en) | Acrylic polyurethane coatings including polyether polyols | |
| CN104479103B (en) | Polyurethane curing agent having high functionality, preparation method and use thereof | |
| CN117887037A (en) | Biuret polyisocyanate composition and preparation method thereof | |
| US4388245A (en) | Process for preparing organic polyisocyanate compositions | |
| CN110790895B (en) | Aliphatic polyisocyanate composition, preparation method thereof and coating composition | |
| EP1443064B1 (en) | Polyisocyanate polyaddition composition and powder coating material | |
| CN114507332B (en) | Polyisocyanate containing biuret structure and preparation method thereof | |
| CN116751356A (en) | Polyisocyanate composition, preparation method and application thereof | |
| CN116120801A (en) | Double-component modified polyurethane emulsion for metal surface and preparation method thereof | |
| CN117683205A (en) | Biuret polyisocyanate composition and preparation method thereof | |
| CN117534816A (en) | Polyisocyanate composition, preparation method and coating composition | |
| CN116444764A (en) | Low-viscosity high-functionality biuret polyisocyanate composition and preparation method thereof | |
| CN114163609A (en) | Polyisocyanate composition, preparation method thereof and coating composition | |
| EP4166589A1 (en) | Isocyanurate-containing polyisocyanate composition with stable chromaticity, and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |