CN105566239A - Preparation method of aliphatic diisocyanate tripolymer curing agent - Google Patents

Preparation method of aliphatic diisocyanate tripolymer curing agent Download PDF

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Publication number
CN105566239A
CN105566239A CN201510937619.XA CN201510937619A CN105566239A CN 105566239 A CN105566239 A CN 105566239A CN 201510937619 A CN201510937619 A CN 201510937619A CN 105566239 A CN105566239 A CN 105566239A
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China
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aliphatic diisocyanate
curing agent
reaction
diisocyanate trimer
aliphatic
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CN201510937619.XA
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Chinese (zh)
Inventor
杨霞
魏其凡
郑世清
徐进
付振波
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QINGDAO YKHY PROCESS AND INFORMATION TECHNOLOGY Co Ltd
YINGUANG CHEMICAL INDUSTRY GROUP Co Ltd GANSU
Qingdao University of Science and Technology
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QINGDAO YKHY PROCESS AND INFORMATION TECHNOLOGY Co Ltd
YINGUANG CHEMICAL INDUSTRY GROUP Co Ltd GANSU
Qingdao University of Science and Technology
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Priority to CN201510937619.XA priority Critical patent/CN105566239A/en
Publication of CN105566239A publication Critical patent/CN105566239A/en
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D251/00Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12Heterocyclic 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
    • C07D251/26Heterocyclic 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
    • C07D251/30Only oxygen atoms
    • C07D251/34Cyanuric or isocyanuric esters
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/77Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78Nitrogen
    • C08G18/79Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04Polyurethanes

Abstract

The invention discloses a preparation method of an aliphatic diisocyanate tripolymer curing agent. The preparation method is characterized by comprising the following steps of adding aliphatic diisocyanate monomers into a reactor under the protection of inert gas; adding homemade trimerization catalysts for performing self-polymerization to generate aliphatic diisocyanate tripolymers; adding terminating agents to terminate the reaction after the proper conversion rate is reached; filtering and collecting clear filtering liquid to be used as raw products; using a short-process evaporator to perform twice separation on the crude product; recovering and reusing unreacted free monomers, wherein the content of the free monomers in the separated aliphatic diisocyanate tripolymers is reduced to be lower than 0.4 percent. The aliphatic diisocyanate tripolymers prepared by the preparation method can be prepared into super fast-drying paint; good anti-yellowing performance is realized; the aliphatic diisocyanate tripolymers can be widely applied to high-grade paint.

Description

A kind of preparation method of aliphatic diisocyanate trimer curing agent
Technical field
The present invention relates to a kind of preparation method of polyurethane curing agent of non yellowing, particularly a kind of preparation method of aliphatic diisocyanate trimer curing agent.
Background technology
Urethane has excellent physical and mechanical properties and chemical-resistant stability, is widely used in every field.And as the main raw material of urethane, the aliphatic isocyanates advantage maximum compared with aromatic isocyanate is that the aliphatic isocyanates Trimeric structures that synthesizes does not have reactive hydrogen atom, can not be formed in molecule or intermolecular hydrogen bonding, thus the viscosity of product is lower, and there is good corrosion resistance nature and yellowing resistance energy, can be used in high-grade paint.
Hexamethylene diisocyanate is the typical aliphatic isocyanates of application, its steam forces down, volatility is large, construction toxic is also large, directly can not be used as the solidifying agent in coating, generally hexamethylene diisocyanate is processed into the affixture of low volatility, biuret or tripolymer and is applied to polyurethane coating, most hexamethylene diisocyanates comes into the market with trimerical form, and tripolymer is the twice of biuret consumption on the market.
But China all lags far behind American-European and Japan in the production of hexamethylene diisocyanate class solidifying agent and research field and waits state, this series products all dependence on import needed for domestic.The reason hindering domestic hexamethylene diisocyanate class solidifying agent to realize producing mainly contains 3 points: one is that raw material sources rely on import; Two is because hexamethylene diisocyanate two isocyanate-reactive are identical, and very easily generate degree of depth polymkeric substance or gelation, manufacturing technique requirent is higher, and operation easier is large; Three is that the separating device removing excessive free monomer is invested large, and technology difficulty is large, and running cost is high.
Hexamethylene diisocyanate is under catalyst action, and the mutual addition of isocyanate group, causes polyreaction, and reaction exists various active intermediate, can form different reaction product.With the change of ambient conditions, in hexamethylene diisocyanate autohemagglutination product, the massfraction of each component is different, and isocyano massfraction is also variant.The autohemagglutination product of hexamethylene diisocyanate has tripolymer, dimer, carbodiimide, linear polymer and cyclic multimeric etc.
The use of catalyzer plays very important effect in trimerization reaction, the viscosity of its major effect product, color and luster, polymerizing condition and product performance.The result of catalyzed reaction should make the transformation efficiency of trimerization reaction high, and in product, the product of high molecular and dimer reduce as far as possible.
US Patent No. 00969 report hexamethyldisilazane makes the technique that catalyst hexamethylene diisocyanate carries out trimerization reaction, but require that temperature of reaction is 120 DEG C, high temperature easily causes the xanthochromia of hexamethylene diisocyanate, the aliphatic diisocyanate tripolymer colourity of preparation is easy to exceed standard, and is not suitable for for high-grade paint.
Chinese patent CN103435778A uses the isocyanate trimerization catalyst catalysis hexamethylene diisocyanate containing 2-hydroxyalkyl quaternary ammonium bases to prepare aliphatic diisocyanate tripolymer, it is easy that this catalyzer has synthesis, steadily, catalytic efficiency is high in effect, the advantage such as can to have an effect in room temperature.But there is more cyclic multimeric in the autohemagglutination product of quaternary ammonium hydroxide catalysis, catalytic activity is larger, and its polarity is very strong, in isocyanic ester, solubleness is low, is easily gathered into block after adding reactor, is attached on agitator arm and reactor wall, cause catalyst member inactivation, or make the concentration of catalyzer local too high, cause the homogeneity of reaction bad, in product, have gel piece to be formed.
US Patent No. 4324879 reports N, N, N-trimethylammonium-N-(2-hydroxyethyl) quaternary ammonium hydroxide, N, N, the ethylhexanol solution of N-trimethylammonium-N-(2-hydroxypropyl) quaternary ammonium hydroxide is made catalyst hexamethylene diisocyanate and is carried out trimerization reaction, the tripolymer of low viscosity, low-monomer-content can be prepared, but solvent add the cost increasing recycling design.
Chinese patent CN104447413A uses tri-n-butyl phosphine catalyst hexamethylene diisocyanate to prepare aliphatic diisocyanate tripolymer, it is low that this catalyzer has technological reaction temperature, catalytic efficiency is high, the advantages such as the reaction times is short, and the aliphatic diisocyanate trimer curing agent colourity obtained is low.But higher by the product viscosity of this catalyst preparing, and decline with NCO content, product viscosity rises very fast, and catalyzer is dissolved in performed polymer simultaneously, is unfavorable for monomer separation and product stock.
The silicoorganic compound that US Patent No. 20030109665A1 report heptamethyldisilazane and tetrabutylammonium fluorochemical synthesize carry out hexamethylene diisocyanate trimerization reaction as catalyzer, compared with making catalyzer with traditional aminosilane based compound, this catalyzer has higher catalytic activity, after dropwise adding catalyzer, temperature of reaction can sharply be increased to 210 DEG C, too high temperature of reaction easily causes the xanthochromia of hexamethylene diisocyanate, and product viscosity raises, molecular weight distribution is uneven.
US Patent No. 4960848 report N, N, the 2-ethylhexyl-1 of N-trimethylammonium-N-phenmethyl Neutral ammonium fluoride, the advantages such as the quaternary ammonium fluorides such as the acetonitrile solution of 3-glycol solution, tetrabutyl ammonium fluoride silica gel, tetrabutyl ammonium fluoride make the technique of catalyst trimerization hexamethylene diisocyanate, and this catalyzer has than other metallic compounds and silicoorganic compound catalyst removal is easy, refining cost is low, product colour is shallow.But higher by the product viscosity of this catalyst preparing, and decline with NCO content, product viscosity rises very fast.In addition the product that this catalyzer generates when catalytic trimerization hexamethylene diisocyanate has turbid phenomenon, is not suitable for painting for surface.And the reaction times is longer, about 24h.
The object of the invention is to overcome the deficiencies in the prior art, a kind of preparation method for being prepared substantially colourless aliphatic diisocyanate trimer curing agent with good quality and circulation ratio by very simple technique is provided, the present invention is particularly in the generation avoiding pentamer, heptamer as much as possible, the aliphatic diisocyanate trimeric molecules mass distribution obtained is narrow, the content of free isocyanate is low, thus improves the trimerical quality of aliphatic diisocyanate and productive rate.
Summary of the invention
Technical problem to be solved by this invention overcomes the deficiencies in the prior art, provides a kind of preparation method of aliphatic diisocyanate trimer curing agent.
For achieving the above object, the present invention adopts following technical scheme:
A kind of aliphatic diisocyanate tripolymer, it represents with following structural formula:
A preparation method for aliphatic diisocyanate trimer curing agent, the method step is:
(1) under protection of inert gas, aliphatic diisocyanate monomer is dropped in reactor, stir and be warming up to 50 DEG C ~ 80 DEG C, the isocyanate trimerization catalyst adding the self-control quaternary ammonium salt accounting for aliphatic diisocyanate monomer mass 0.1% ~ 0.3% for three times is divided in 0.5 ~ 1h, temperature of reaction controls at 50 DEG C ~ 80 DEG C, reaction 2h ~ 6h, every the mass percentage of 1 hour assaying reaction system free monomers and NCO group;
(2) when the mass percentage of the NCO group recording reaction system is 40% ~ 45%, now aliphatic diisocyanate transformation efficiency is 20% ~ 40%, add the isocyanate trimerization stopper termination reaction accounting for aliphatic diisocyanate monomer mass 0.1% ~ 1%, insulation 0.5 ~ 1h, filters and collects clear filtrate as thick product;
(3) the aliphatic diisocyanate tripolymer prepolymer obtained is entered tripping device by the input speed of 0.1 ~ 2 l/h by sparger, the first time lock out operation temperature of tripping device controls to be 150 ~ 200 DEG C, it is 100 ~ 200PaA that working pressure controls, second time lock out operation temperature controls to be 150 ~ 200 DEG C, it is 10 ~ 20PaA that working pressure controls, obtain the aliphatic diisocyanate trimer curing agent product that free monomer is down to less than 0.4% after separation, the light constituent of clear is reused after detection analysis is qualified.
Described aliphatic isocyanates is hexamethylene diisocyanate and/or 3-isocyanic ester methylene-3,5,5-trimethylcyclohexylisocyanate.
Described catalyzer is self-control quaternary ammonium salt, its preparation method is for be dissolved in organic solvent by quaternary ammonium hydroxide compounds, carboxylation is carried out again with the carboxylic acid compound of the equimolar amount be dissolved in organic solvent, stirring makes reaction carry out completely, through gas chromatographic analysis, do not occur that peak is considered as reaction end to carboxylic acid compound, underpressure distillation removing organic solvent obtains quaternary ammonium salt catalyst for trimerization.
Described quaternary ammonium hydroxide is Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide.
Described organic acid is sad, lactic acid, 2-ethyl-2-hydroxybutyric acid, 2-hydroxy isocaproic acid.
Described organic solvent is methyl alcohol, ethanol.
Described terminator is phosphoric acid, Benzoyl chloride, para Toluic Acid.
Described tripping device is inner-cooled short-path evaporator or external-cooling type thin-film evaporator.
Compared with prior art, beneficial effect of the present invention is:
(1) catalyzer is easy to preparation, excellent catalytic effect, reacting balance, and circulation ratio is better; ;
(2) input speed of control short-path evaporator, jacket temperature and vacuum tightness is passed through, the load of Absorbable organic halogens short-path evaporator, material is made at high temperature to have the suitable residence time, the colourity avoiding long-time heat to cause raises, material is scattered in film rapidly by the sparger of short-path evaporator, increase heat transfer area, and condition of high vacuum degree enhances the evaporation of monomer, free monomer can be down to less than 0.4%, and light constituent is recycled after analyzing after testing;
(3) the trimer curing agent product water white transparency prepared, even molecular weight distribution, obtained coating film gloss is stablized.
Accompanying drawing explanation
Fig. 1 prepares aliphatic diisocyanate tripolymer process flow diagram.Wherein, 1, reactor, 2, discharging pump, 3, strainer, 4, mixture storage tank, 5, volume pump, 6, short-path evaporator, 7, work in-process storage tank, 8, Leng Jing, 9, vacuum pump, 10, finished product storage tank, 11, HDI fresh feed pump, 12, raw material HDI storage tank, 13, rectifying HDI storage tank, 14, recovery pump.
Embodiment
In order to implement the present invention better, further illustrate the present invention below by embodiment, but the present invention is not limited thereto.
Embodiment 1
1000gHDI is added to in the reactor 1 stirred, stir, logical nitrogen, heating is temperature control 65 DEG C also, divide in 1h after temperature-stable and add sad tetramethyl-ammonium salt catalyst from reactor 1 tapping three times, catalyzer total amount is 0.1% of aliphatic diisocyanate monomer mass, from adding catalyzer, every the mass percentage of 1 hour sampling and measuring reaction system free monomers and NCO group, add the Benzoyl chloride terminator termination reaction of aliphatic diisocyanate monomer mass 0.1% from reactor 1 tapping when the mass percentage of the NCO group recording reaction system is 40%, strainer 3 is sent into by discharging pump 2 after insulation 1h, mixture storage tank 4 is entered after filtering out most of solid particulate.
The prepolymer of mixture storage tank 4 enters short-path evaporator 6 by the input speed of 1 l/h by sparger through volume pump 5, short-path evaporator 6 first time lock out operation temperature controls to be 160 DEG C, it is 100 ~ 200PaA that working pressure controls, free monomer can reduce to 2% by 70% when entering, be separated the prepolymer obtained through short-path evaporator 6 for the first time and directly enter work in-process storage tank 7 by gravity, pending second time is separated; The prepolymer of work in-process storage tank 7 enters short-path evaporator 6 by the input speed of 1 l/h by sparger through volume pump 5, short-path evaporator 6 second time lock out operation temperature controls to be 160 DEG C, it is 10 ~ 20PaA that working pressure controls, obtain the aliphatic diisocyanate trimer curing agent product that free monomer is down to less than 0.4% after separation and directly enter finished product storage tank 10 by gravity, the light constituent of the clear that twice separation obtains directly enters rectifying HDI storage tank 13 by gravity, analyze after testing qualified after send into raw material HDI storage tank 12 through recovery pump 14 and reuse.Working pressure is controlled by vacuum pump 9, and the light constituent HDI taken out of enters rectifying HDI storage tank 13 by after the condensation of cold well 8.
Embodiment 2
1000gHDI is added to in the reactor 1 stirred, stir, logical nitrogen, heating is temperature control 65 DEG C also, divide in 1h after temperature-stable and add lactic acid tetramethyl-ammonium salt catalyst from reactor 1 tapping three times, catalyzer total amount is 0.1% of aliphatic diisocyanate monomer mass, from adding catalyzer, every the mass percentage of 1 hour sampling and measuring reaction system free monomers and NCO group, add the Benzoyl chloride terminator termination reaction of aliphatic diisocyanate monomer mass 0.1% from reactor 1 tapping when the mass percentage of the NCO group recording reaction system is 40%, strainer 3 is sent into by discharging pump 2 after insulation 1h, mixture storage tank 4 is entered after filtering out most of solid particulate.
The prepolymer of mixture storage tank 4 enters short-path evaporator 6 by the input speed of 1 l/h by sparger through volume pump 5, short-path evaporator 6 first time lock out operation temperature controls to be 160 DEG C, it is 100 ~ 200PaA that working pressure controls, free monomer can reduce to 2% by 70% when entering, be separated the prepolymer obtained through short-path evaporator 6 for the first time and directly enter work in-process storage tank 7 by gravity, pending second time is separated; The prepolymer of work in-process storage tank 7 enters short-path evaporator 6 by the input speed of 1 l/h by sparger through volume pump 5, short-path evaporator 6 second time lock out operation temperature controls to be 160 DEG C, it is 10 ~ 20PaA that working pressure controls, obtain the aliphatic diisocyanate trimer curing agent product that free monomer is down to less than 0.4% after separation and directly enter finished product storage tank 10 by gravity, the light constituent of the clear that twice separation obtains directly enters rectifying HDI storage tank 13 by gravity, analyze after testing qualified after send into raw material HDI storage tank 12 through recovery pump 14 and reuse.Working pressure is controlled by vacuum pump 9, and the light constituent HDI taken out of enters rectifying HDI storage tank 13 by after the condensation of cold well 8.
The aliphatic diisocyanate tripolymer product analysis result that above two embodiments obtain is as follows:
Index name Unit Index
-NCO% % <21.0
Free monomer % % <0.2
Hydrolyzable chlorine ppm <80
Colourity Hz <50
Viscosity cP ≈3500
Acidity ppm ≈8
Reclaim the index of monomer:
Index name Unit Index
Composition % >99
Acidity % <0.005
Hydrolysis chlorine % <0.01
Colourity Hz <15

Claims (8)

1. a preparation method for aliphatic diisocyanate trimer curing agent, described in it, method is as follows:
(1) under protection of inert gas, aliphatic diisocyanate monomer is dropped in reactor, stir and be warming up to 50 DEG C ~ 80 DEG C, the isocyanate trimerization catalyst adding the self-control quaternary ammonium salt accounting for aliphatic diisocyanate monomer mass 0.1% ~ 0.3% for three times is divided in 0.5 ~ 1h, temperature of reaction controls at 50 DEG C ~ 80 DEG C, reaction 2h ~ 6h, every the mass percentage of 1 hour assaying reaction system free monomers and NCO group;
(2) when the mass percentage of the NCO group recording reaction system is 40% ~ 45%, now aliphatic diisocyanate transformation efficiency is 20% ~ 40%, add the isocyanate trimerization stopper termination reaction accounting for aliphatic diisocyanate monomer mass 0.1% ~ 1%, insulation 0.5 ~ 1h, filters and collects clear filtrate as thick product;
(3) the aliphatic diisocyanate tripolymer prepolymer obtained is entered tripping device by the input speed of 0.1 ~ 2 l/h by sparger, the first time lock out operation temperature of tripping device controls to be 150 ~ 200 DEG C, it is 100 ~ 200PaA that working pressure controls, second time lock out operation temperature controls to be 150 ~ 200 DEG C, it is 10 ~ 20PaA that working pressure controls, obtain the aliphatic diisocyanate trimer curing agent product that free monomer is down to less than 0.4% after separation, the light constituent of clear is reused after detection analysis is qualified.
2. a kind of aliphatic diisocyanate trimer preparation method according to claim 1, it is characterized in that, described aliphatic isocyanates is hexamethylene diisocyanate and/or 3-isocyanic ester methylene-3,5,5-trimethylcyclohexylisocyanate.
3. the preparation method of a kind of aliphatic diisocyanate trimer curing agent according to claim 1, it is characterized in that: described catalyzer is self-control quaternary ammonium salt, its preparation method is for be dissolved in organic solvent by quaternary ammonium hydroxide compounds, carboxylation is carried out again with the carboxylic acid compound of the equimolar amount be dissolved in organic solvent, stirring makes reaction carry out completely, through gas chromatographic analysis, do not occur that peak is considered as reaction end to carboxylic acid compound, underpressure distillation removing organic solvent obtains quaternary ammonium salt catalyst for trimerization.
4. the preparation method of a kind of aliphatic diisocyanate trimer curing agent according to claim 3, is characterized in that: described quaternary ammonium hydroxide is Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide.
5. the preparation method of a kind of aliphatic diisocyanate trimer curing agent according to claim 3, is characterized in that: described organic acid is sad, lactic acid, 2-ethyl-2-hydroxybutyric acid, 2-hydroxy isocaproic acid.
6. the preparation method of a kind of aliphatic diisocyanate trimer curing agent according to claim 3, is characterized in that: described organic solvent is methyl alcohol, ethanol.
7. the preparation method of a kind of aliphatic diisocyanate trimer curing agent according to claim 1, is characterized in that: described terminator is phosphoric acid, Benzoyl chloride, para Toluic Acid.
8. the preparation method of a kind of aliphatic diisocyanate trimer curing agent according to claim 1, is characterized in that: described tripping device is inner-cooled short-path evaporator or external-cooling type thin-film evaporator.
CN201510937619.XA 2015-12-16 2015-12-16 Preparation method of aliphatic diisocyanate tripolymer curing agent Pending CN105566239A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108499606A (en) * 2017-02-24 2018-09-07 万华化学集团股份有限公司 A kind of neighbour's sulfydryl aryl N-heterocyclic carbine metal composition catalyst and its preparation method and application
CN110373169A (en) * 2019-07-19 2019-10-25 中国石油集团川庆钻探工程有限公司 Solidification oil base leak stopping slurry and preparation method thereof when controllable
CN110396398A (en) * 2019-07-19 2019-11-01 中国石油集团川庆钻探工程有限公司 Superhigh temperature oil base drilling fluid temperature control type curing agent and preparation method thereof
CN110408372A (en) * 2019-07-19 2019-11-05 中国石油集团川庆钻探工程有限公司 Middle low temperature oil base solidification leak stopping slurry and preparation method thereof
CN110437810A (en) * 2019-07-19 2019-11-12 中国石油集团川庆钻探工程有限公司 Cross-linking oil base drilling fluid curing agent of pressure sensitive and preparation method thereof
WO2020097950A1 (en) * 2018-11-12 2020-05-22 万华化学集团股份有限公司 Preparation method of polyisocyanate

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US5691440A (en) * 1995-10-05 1997-11-25 Arco Chemical Technonogy, L.P. Catalyst and process for producing isocyanate trimers
CN103435778A (en) * 2013-08-27 2013-12-11 华南理工大学 Preparation method of hexamethylene diisocyanate tripolymer curing agent
CN104250363A (en) * 2013-06-28 2014-12-31 旭化成化学株式会社 Polyisocyanate composition

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US4324879A (en) * 1978-09-08 1982-04-13 Bayer Aktiengesellschaft Process for the preparation of polyisocyanates containing isocyanurate groups and the use thereof
US5691440A (en) * 1995-10-05 1997-11-25 Arco Chemical Technonogy, L.P. Catalyst and process for producing isocyanate trimers
CN104250363A (en) * 2013-06-28 2014-12-31 旭化成化学株式会社 Polyisocyanate composition
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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108499606A (en) * 2017-02-24 2018-09-07 万华化学集团股份有限公司 A kind of neighbour's sulfydryl aryl N-heterocyclic carbine metal composition catalyst and its preparation method and application
CN108499606B (en) * 2017-02-24 2020-11-20 万华化学集团股份有限公司 O-mercapto aryl nitrogen heterocyclic carbene metal complex catalyst and preparation method and application thereof
WO2020097950A1 (en) * 2018-11-12 2020-05-22 万华化学集团股份有限公司 Preparation method of polyisocyanate
CN110373169A (en) * 2019-07-19 2019-10-25 中国石油集团川庆钻探工程有限公司 Solidification oil base leak stopping slurry and preparation method thereof when controllable
CN110396398A (en) * 2019-07-19 2019-11-01 中国石油集团川庆钻探工程有限公司 Superhigh temperature oil base drilling fluid temperature control type curing agent and preparation method thereof
CN110408372A (en) * 2019-07-19 2019-11-05 中国石油集团川庆钻探工程有限公司 Middle low temperature oil base solidification leak stopping slurry and preparation method thereof
CN110437810A (en) * 2019-07-19 2019-11-12 中国石油集团川庆钻探工程有限公司 Cross-linking oil base drilling fluid curing agent of pressure sensitive and preparation method thereof
CN110437810B (en) * 2019-07-19 2021-06-11 中国石油集团川庆钻探工程有限公司 Curing agent for pressure-sensitive crosslinkable oil-based drilling fluid and preparation method thereof
CN110396398B (en) * 2019-07-19 2021-07-23 中国石油集团川庆钻探工程有限公司 Temperature control type curing agent for ultra-high temperature oil-based drilling fluid and preparation method thereof
CN110373169B (en) * 2019-07-19 2021-07-23 中国石油集团川庆钻探工程有限公司 Time-controllable solidified oil-based leakage-stopping slurry and preparation method thereof
CN110408372B (en) * 2019-07-19 2021-08-13 中国石油集团川庆钻探工程有限公司 Medium-low temperature oil-based solidified leakage-stopping slurry and preparation method thereof

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Application publication date: 20160511