CN109651278A - A kind of preparation method of polyisocyanates - Google Patents
A kind of preparation method of polyisocyanates Download PDFInfo
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- CN109651278A CN109651278A CN201811344978.4A CN201811344978A CN109651278A CN 109651278 A CN109651278 A CN 109651278A CN 201811344978 A CN201811344978 A CN 201811344978A CN 109651278 A CN109651278 A CN 109651278A
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D273/00—Heterocyclic compounds containing rings having nitrogen and oxygen atoms as the only ring hetero atoms, not provided for by groups C07D261/00 - C07D271/00
- C07D273/02—Heterocyclic compounds containing rings having nitrogen and oxygen atoms as the only ring hetero atoms, not provided for by groups C07D261/00 - C07D271/00 having two nitrogen atoms and only one oxygen atom
- C07D273/04—Six-membered rings
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- 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
- C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
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- 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
- C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
- C08G18/022—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only the polymeric products containing isocyanurate groups
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- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a kind of methods for preparing polyisocyanates, and isocyanates is carried out self-polymeric reaction under the catalysis of fluorinated catalyst, and terminator termination reaction is added after the reaction was completed and obtains reaction solution；Polyisocyanates will be obtained after the removing of unreacted isocyanate-monomer；Fluorine content control in the polyisocyanates is not higher than 80ppm.Fluorine content in method control product of the invention, avoids the turbid phenomenon when storage of product low temperature, and the toxicity, equipment harmfulness and downstream that fluorine is also effectively reduced in internal system endanger.
Description
Technical field
The present invention relates to a kind of preparation methods of polyisocyanate curing agent product.
Background technique
Polyisocyanates of the aliphatic diisocyanate monomer by polymerization preparation, oneself is widely used in polyurethane coating
Or adhesive industry can effectively reduce volatile isocyanate-monomer to the harmfulness of the person by isocyanates self-polymerization.
Isocyanate-monomer can be obtained urea diketone (structural formula 1), tripolymer (structural formula 2), imino group and be disliked by polymerization
Oxadiazinediones (structural formula 3), three kinds of structures respectively have feature, influence the performance of product.Urea diketone viscosity is minimum, and degree of functionality is small, and three
Aggressiveness degree of functionality is big, and viscosity is big, and imino group oxadiazines diketone viscosity is less than tripolymer, and degree of functionality is greater than urea diketone, viscosity
Small to be convenient for construction, degree of functionality is conducive to solidify greatly.
For the existing method for preparing polyisocyanates by wide coverage, the catalyst used mainly has alkylphosphines, fluorine
For acid compound, triazole salt compound, polyfluoro salt dissolving, fluoride salt etc., for example, being described in US5914383A and CN1243124A
It is the polyisocyanates that catalyst preparation contains imino group oxadiazines diketone with polyfluoro salt dissolving, wherein imino group oxadiazines diketone
Content is high, and product turbidity is higher (being greater than 1NTU).
Patent US4937339 uses fluoride salt complex quaternary ammonium salts and polyethylene oxide to prepare polyisocyanates, but
Wherein imino group oxadiazines diketone content is low, and tripolymer too high levels, product viscosity is larger, refers to be easy in reaction process
Generate agglomerated particle.
US7595396 prepares the polyisocyanates of imido- oxadiazines diketone, gained using fluoracid ionic catalyst
Product imino group oxadiazines diketone content it is high, but insoluble matter is easy to appear in product.
It is high that the method that US6107484 proposes fluoride salt protonation solvent is prepared for imino group oxadiazines diketone content
Polyisocyanates, but be still required to introduce fluorine in catalyst, it is repeatedly referred in embodiment and is easy to appear insoluble matter in reaction process.
In the prior art, the polyisocyanate product fluorine content one that catalysis is prepared is carried out using fluorinated catalyst
As in 150-200ppm.Patent disclosed above, which is directed to, uses fluorine in the preparation process of polyisocyanates, obtained production
Product are easy to happen precipitation phenomenon in low-temperature storage, generate insoluble matter, for example at -20 DEG C, therefore, the said goods are unfavorable for cold
The downstream Client application in area.
Summary of the invention
In view of this, the present invention provides a kind of preparation method of polyisocyanates, this method be can be effectively reduced in product
Fluorine content, product low-temperature stability can be substantially improved, avoid product low temperature storage when turbid phenomenon, can also be effective
The toxicity, equipment harmfulness and downstream that fluorine is reduced in internal system endanger.
In order to achieve the object of the present invention, present invention employs the following technical solutions:
The present invention provides a kind of methods for preparing polyisocyanates, by isocyanates under the catalysis of fluorinated catalyst
Self-polymeric reaction is carried out, terminator termination reaction is added after the reaction was completed and obtains reaction solution；Unreacted isocyanate-monomer is taken off
Polyisocyanates is obtained after removing；
Fluorine content control in the polyisocyanates is not higher than 80ppm.
In preparation process of the invention, it is preferable that the reaction solution terminated after reacting is cooled to -30~30 DEG C, is used in combination
Fluorinated material carries out absorption or filtration treatment, for example, -10 DEG C, 0 DEG C, 10 DEG C.In isocyanates raw material mainly include carbon, hydrogen,
Oxygen, nitrogen, and fluorine-containing compound (fluorine phase compound) and not fluorine-containing compound (hydrocarbon phase compound) in temperature be-
Compatibility is worse under conditions of 30~30 DEG C, is more conducive to removing fluorine class substance in filtering or adsorption process using fluorine material.
Fluorinated material is for example, can be used polytetrafluoroethylene (PTFE) filter bag, polytetrafluoroethylene (PTFE) filter core or polytetrafluoroethylene packing；By using
Fluorinated material carries out absorption or filtration treatment further decreases fluorine and filters out in reaction solution in the dissolubility of reaction solution, and effectively
Fluorine class substance.
In preparation process of the invention, the different self-polymeric reaction of conversion ratio can obtain the different product of performance, some
In preferred embodiment, when the conversion ratio of the self-polymeric reaction is 20%~50%, the fluorinated is added and terminates
The molar content of imino group oxadiazines diketone group and isocyanurate group rubs in the polyisocyanates that agent can make
You control 0.5~1.5, further preferably 1.0~1.4, for example, 1.1,1.2 content.It specifically can be during the preparation process
Quantitative calculating is carried out by content of the gel chromatography technology to isocyanates, as the judgment criteria of reaction conversion ratio, when obtaining
When the conversion ratio of self-polymeric reaction is 20%~50%, imino group in the polyisocyanates that fluorine-containing terminator can make is added and dislikes
The molar content of oxadiazinediones group and the molar content of isocyanurate group control in above range, and obtained product glues
Spend it is small, convenient for construction, during downstream application have unique advantage.
In the preparation process in accordance with the present invention, the terminator used is fluorinated terminator.In some specific embodiments
In, the fluorinated terminator has the structure such as following formula (I):
CnF2n+1(CH2)xO(CH2CH2O)mH formula (I)
Wherein, n is the integer of 1-10, preferably 2-6；
M is the integer of 1-15, preferably 3-8；
X is 0,1,2,3.
In the structure of above formula (I), it can be more preferably 4,5,7 that n, which can be more preferably 3,4,5, m,.
The terminator of above structure can be obtained using known preparation method by reaction addition polymerization as follows:
Preparation method of the invention is by fluorine-containing terminator and containing the collective effect of fluorine catalyst, hence it is evident that reduces fluorine in product
Content.Belong to surfactant substance, present invention in isocyanates raw material containing fluorine catalyst and fluorine-containing terminator
People's discovery, the two is mainly in surface enrichment during the reaction, and very easy contact is simultaneously reacted, and terminator and catalyst are mutually reciprocal
It answers and leads to catalyst inactivation, and then generate the fluorine class substance of more macromolecular, fluorinated terminator using the above structure is opposite
In individual fluorine ion, it is easier to be filtered or be adsorbed, to be more conducive to the fluorine content in control isocyanates.
Method of the invention can generate the bigger fluorine molecule that contains, benefit based on fluorinated terminator and fluorinated catalyst
Increase incompatibility with low temperature；Meanwhile when carrying out absorption and filtration treatment to the reaction solution after reaction, " phase patibhaga-nimitta is utilized
Appearance " principle, fluorinated material such as solid-state polytetrafluoro material can adsorb and remove fluorine class substance, improve the removal efficiency of fluorine,
Create a further reduction the fluorine content in product.
In the preparation process in accordance with the present invention, the fluorinated catalyst preferably selects the structure such as following formula (II):
Wherein, R1、R2、R3、R4It is same or different, separately it is selected from the C of linear chain or branched chain1~C15Alkyl, than
Such as, methyl, propyl, butyl, C7~C15Aralkyl in hydrogen atom on phenyl ring replaced by any group, preferably by alkyl or
Naphthenic base replaces, for example, tolyl, ethylbenzene and butylbenzene base or C6~C12Aryl in hydrogen atom on phenyl ring by any base
Group replaces, and is preferably replaced by alkyl or cycloalkyl, for example, phenyl, diphenyl；
Z is selected from N or P；
Y is selected from fluorine or polyfluoro ion (F (HF)n)-, wherein the integer that n is 1~10, preferably 3-8, for example, 4,5,6.
In the preparation process in accordance with the present invention, by the quality of the isocyanates in terms of, the use of the fluorinated catalyst
Amount preferably 10~1000ppm, further preferably 15~500ppm, more preferably 20~100ppm, for example, 50ppm,
80ppm；The molar ratio of the terminator and the fluorinated catalyst amount is preferably 1:1~2:1, and further preferably 1:
1~1.5:1, for example, 1:1~1.2:1,1:1~1.4:1.
In the preparation process in accordance with the present invention, catalyst can be in undiluted or dissolution use in a solvent.All solvents have
Catalyst soluble and do not decompose and do not react with isocyanates or be formed only into completely when reacting with isocyanates polyurethane
The characteristics of non-destructive downstream product often having in chemistry, the non-destructive downstream product include carbamate, urea groups
Formic acid esters etc..Preferably, the catalyst is preferably added in the form of a solution to reaction system, the catalyst preferably molten
Agent is one of methanol, ethyl alcohol, isobutanol, hexanol, the tert-butyl alcohol, 1,4-butanediol or a variety of；The concentration of catalyst solution is
10~90wt%, preferably 30~80wt%, for example, 40wt%, 60wt%.
In the preparation process in accordance with the present invention, fluorine content is preferably 50%~80% in the fluorinated material of use, excellent
It is selected as 60%~70%, for example, 63%, 67%, fluorine content described herein refers to mass content shared by fluorine；Preferably, institute
Stating fluorinated material is solid-state fluorinated material, preferably polytetrafluoroethylene material, is further preferably had such as following formula (III)
Structure:
[CF2-CF2]nFormula (III)
Wherein, n is 100~100000, further preferably 200~5000, more preferably 500~3000, for example, 600,
1000,2000.
It is further preferred that the fluorinated material is polytetrafluoroethylene (PTFE) filter bag, polytetrafluoroethylene (PTFE) filter core or polytetrafluoroethyl-ne
Alkene filler；
It is highly preferred that the aperture of the polytetrafluoroethylene (PTFE) filter bag and polytetrafluoroethylene (PTFE) filter core is between 5-100um, preferably
10-50um, for example, 20um, 40um, the partial size of the polytetrafluoroethylene packing is 0.5~1.5mm, preferably 0.7~
1.3mm, for example, 1mm, 1.2mm.
In the preparation process in accordance with the present invention, the isocyanates raw material is preferably C4~C20Aliphatic diisocyanate,
C4~C20Alicyclic diisocyanate and C6~C20One of aromatic diisocyanate or a variety of；
It is further preferred that the isocyanates raw material be hexamethylene diisocyanate, pentamethylene diisocyanate,
2- methylpentane -1,5- diisocyanate, 1,3- bis- (isocyanatomethyl) hexamethylene, (the isocyanato- first of Isosorbide-5-Nitrae-two
Base) hexamethylene, norboneol alkyl dimethyl isocyanates, 2,2,4- trimethyl hexamethylene diisocyanates, 2,4,4- trimethyls oneself two
Isocyanates and 4, one of 4'- dicyclohexyl methyl hydride diisocyanate or a variety of.
Above-mentioned isocyanates raw material is prepared pair in which way the preparation method is that inessential, including
The monomer that can be used or produced without using phosgene or other any methods.
In the preparation process in accordance with the present invention, the self-polymeric reaction carries out under the protection of inert gas, the self-polymeric reaction
Temperature be 10~100 DEG C, further preferably 40~80 DEG C, for example, 50 DEG C, 60 DEG C；The inert gas is preferably nitrogen
And/or argon gas.
In preparation method of the invention, thin film evaporation, molecular distillation or the mode of extraction is selected to remove unreacted isocyanide
Acid ester monomer；Specifically, the temperature of the thin film evaporation is 130~160 DEG C, and the temperature of the molecular distillation is 140~150
DEG C, the solvent used that extracts is selected from hydrocarbon solvent, for example, n-hexane and hexamethylene.
In addition, during preparation method of the invention some additions can be inserted in the product according to the demand in downstream
Agent, to improve the performance of product, for example, addition sterically hindered phenol (2,6- di-t-butyl toluene, 4- methyl -2,6- di-t-butyl first
Benzene) it is used as antioxidant, the problem of to improve product color；It adds hindered amine light stabilizer (HALS) and is used as light stabilizer, to have
Effect inhibits photooxidative degradation.
Fluorine content is not higher than 80ppm in the polyisocyanates controlled using preparation method of the invention；It is further excellent
The content of fluorine is selected as not higher than 50ppm, more preferably not above 30ppm.
Described fluorine content specifically refers to the mass content shared by fluorine in the product of polyisocyanates in the present invention, described
Fluorine include ionic state fluorine form, hydration fluorine ion form or covalent state fluorine form.
Compared with prior art, the invention has the following advantages that
The present invention enhances the turbid of final products by introducing fluorinated catalyst self-polymeric reaction during the preparation process
The low-temperature stability of degree avoids product from turbid phenomenon occur in low temperature storage.
Using polyisocyanates made from preparation method of the invention, fluorine content exists in 80ppm hereinafter, fluorine is effectively reduced
System toxicity, equipment harmfulness and downstream harm inside system.The harm for obviously controlling fluorine, reduces monomer reuse process
In fluorine accumulate problem.
Specific embodiment
Technical solution of the present invention and its effect are described further below by way of specific embodiment.It should be appreciated that following
Embodiment is merely to illustrate the contents of the present invention, the protection scope being not intended to restrict the invention.Using design pair of the invention
The simple change that the present invention carries out is all within the scope of the claimed invention.
Following test method is used in the embodiment of the present invention:
The content test method of monomer in isocyanates raw material: standard GB/T/T 18446-2009 is used；
The measuring method of the content (mol%) of imino group oxadiazines diketone, isocyanuric acid ester, urea diketone: by the matter integrated
Son uncouple 13C H NMR spectroscopy (being obtained on Bruker DPX-400 instrument) calculate and be based respectively on the existing isocyanuric acid
Ester, imino group oxadiazines diketone, urea diketone summation meter；Each structural element has following chemical shift (indicating with ppm):
Imino group oxadiazines diketone: 147.8,144.3 and 135.3；Isocyanuric acid ester: 148.4；Urea diketone: 157.1；
The detection of fluorine element: using Oxygen Bomb Combustion-chromatography of ions test；
It carries out raw material diisocyanate monomer using gel chromatography technology to quantify, as judging that reaction conversion ratio (is based on
The different propylhomoserin vinegar monomer mass of raw material two calculate) monitoring means；Using following Coupled columns: LC-20AD/RID-10A, color
Spectrum column be MZ-Gel SDplus 10E3A 5um (8.0 × 300mm), MZ-Gel SDplus 500A 5um (8.0 ×
300mm), MZ-Gel SDplus 100A 5um (8.0 × 300mm), Shimadzu；Mobile phase: tetrahydrofuran；Flow velocity: 1.0mL/
min；Analysis time: 40min；Chromatogram column temperature: 35 DEG C；
Viscosity measurements: it under conditions of temperature is 25 DEG C, is tested using the VT550 viscosimeter that Haak is manufactured.
The information of raw material and detecting instrument equipment in following each embodiments:
Hexamethylene diisocyanate: Wan Hua, wannate HDI, 99%；
Pentamethylene diisocyanate: three wells, STABIO PDI, 98%；
N-hexyl alcohol: sigma-Aldrich, 98%；
N-hexane: sigma-Aldrich, 98%；
Tetramethyl fluoram: sigma-Aldrich, 95%；
Tetrabutyl ammonium fluoride: sigma-Aldrich, 95%；
Polytetrafluoroethylene (PTFE) filter core: section hundred is special, LPF0045D；
Polytetrafluoroethylene (PTFE) filter bag: section hundred is special, LPF0045E；
Polytetrafluoroethylene packing: east fluorination work, PVDF T1；
Tetrabutyl bifluoride phosphine: it is prepared based on the preparation method referred in embodiment 1 in patent CN99109785.8；
Tetrabutyl fluoram: TCL, 95%.
Terminator in following embodiment obtains with the following method:
C2F5CH2O(CH2CH2O)3H: in reaction kettle, at 80 DEG C, the perfluor propyl alcohol (C of 1mol2F5CH2) and 0.001mol OH
Potassium hydroxide mixing, vacuum pressure 1000Pa heat 0.5h, then lay down vacuum, the ethylene oxide of 3.5mol, temperature be added
It rises to 90 DEG C, keeps pressure 0.15MPa, sustained response 2h, then remove remaining ethylene oxide, using PE filter element filtering,
Up to product；
C6F13CH2CH2O(CH2CH2O)4H: in reaction kettle, at 85 DEG C, the perfluorooctanol (C of 1mol6F13CH2CH2OH) with
The potassium hydroxide of 0.001mol mixes, and vacuum pressure 500Pa heats 1h, then lays down vacuum, the ethylene oxide of 4.5mol is added,
Temperature rises to 95 DEG C, keeps pressure 0.2MPa, sustained response 2.5h, remaining ethylene oxide is then removed, using PE filter core
Filtering is to get product；
C3F7CH2O(CH2CH2O)10H: in reaction kettle, at 85 DEG C, the perfluor butanol (C of 1mol3F7CH2OH) with
The potassium hydroxide of 0.001mol mixes, and vacuum pressure 800Pa heats 1h, then lays down vacuum, the ethylene oxide of 11mol is added,
Temperature rises to 90 DEG C, keeps pressure 0.2MPa, sustained response 3h, remaining ethylene oxide is then removed, using PE filter core mistake
Filter is to get product.
Embodiment 1
A) 800g HDI (hexamethylene diisocyanate) is placed in equipped with reflux condensing tube, blender, thermometer and nitrogen
In the round-bottomed flask of gas entrance, the n-hexyl alcohol solution 0.5g of addition 70wt% tetrabutyl bifluoride phosphine after being heated to 70 DEG C, and
It is stirred continuously lower carry out self-polymeric reaction, controls reaction temperature between 70~75 DEG C；When the conversion ratio of monomer in self-polymeric reaction reaches
The C with tetrabutyl bifluoride phosphine equimolar amounts is added when to 30% immediately2F5CH2O(CH2CH2O)3H continues to stir 15min
Terminate reaction；
B) reaction solution after termination is cooled to -20 DEG C, and passes through two-stage polytetrafluoroethylene (PTFE) filter element filtering, above-mentioned poly- four
The aperture 50um of vinyl fluoride filter core；
C) filtered reaction solution is evaporated under conditions of 150 DEG C of temperature, absolute pressure 100Pa using thin film evaporator
The unreacted raw material contained in elimination reaction liquid makes monomer content lower than 0.5wt%, obtains polyisocyanate product.
Through detecting, fluorine element content is 30ppm in the polyisocyanate product that embodiment 1 obtains；Imino group is disliked in product
The viscosity of product is when the ratio between molar content and the molar content of isocyanurate group of oxadiazinediones group are 1,25 DEG C
680cP。
Comparative example 1-1
The process conditions of comparative example 1-1 are same as Example 1, the difference is that: terminator used is chlorobenzoyl chloride.
Through detecting, fluorine element content is 100ppm in the polyisocyanate product that comparative example 1-1 is obtained；Imino group in product
The viscosity of product is when the ratio between molar content and the molar content of isocyanurate group of oxadiazines diketone group are 1,25 DEG C
690cP。
Comparative example 1-2
Comparative example 1-2 process conditions are same as Example 1, the difference is that: it is directly steamed using film after terminating reaction
Hair device evaporates in elimination reaction liquid under 150 DEG C, absolute pressure 100Pa removes unreacted isocyanates.
Through detecting, fluorine element content is 200ppm in the polyisocyanate product that comparative example 1-2 is obtained；Imino group in product
The viscosity of product is when the ratio between molar content and the molar content of isocyanurate group of oxadiazines diketone group are 1,25 DEG C
670cP。
Comparative example 1-3
A) 800g HDI is placed in the round-bottomed flask equipped with reflux condensing tube, blender, thermometer and nitrogen inlet, is added
Heat is to the n-hexyl alcohol solution 0.5g that 70wt% tetrabutyl bifluoride phosphine is added after 70 DEG C, and it is anti-to carry out autohemagglutination under constant stirring
It answers, controls reaction temperature between 70~75 DEG C；It is added and four immediately when the conversion ratio of monomer in self-polymeric reaction reaches 30%
The chlorobenzoyl chloride of butyl bifluoride phosphine equimolar amounts, reaction can be terminated by continuing stirring 15min；
B) reaction solution after termination is steamed under conditions of 150 DEG C of temperature, absolute pressure 100Pa using thin film evaporator
The unreacted raw material contained in hair elimination reaction liquid, makes monomer content lower than 0.5wt%, obtains polyisocyanate product.
Through detecting, fluorine element content is 250ppm in the polyisocyanate product that comparative example 1-3 is obtained；Imino group in product
The ratio between molar content and the molar content of isocyanurate group of oxadiazines diketone group are for 0.9,25 DEG C of product viscosities
710cP。
Embodiment 2
A) 1000g HDI (hexamethylene diisocyanate) is placed in equipped with reflux condensing tube, blender, thermometer and nitrogen
In the round-bottomed flask of gas entrance, the n-hexyl alcohol solution 0.8g of addition 50wt% tetramethyl fluoram after being heated to 60 DEG C, and
It is stirred continuously lower carry out self-polymeric reaction, controls reaction temperature between 60~65 DEG C；When the conversion ratio of monomer in self-polymeric reaction reaches
The C with tetramethyl fluoram equimolar amounts is added when to 40% immediately6F13CH2CH2O(CH2CH2O)4H continues to stir 15min
Reaction can be terminated；
B) reaction solution after termination is cooled to 10 DEG C, and is adsorbed by two-stage polytetrafluoroethylene packing, it is above-mentioned
The partial size of polytetrafluoroethylene packing is 1.0mm；
C) reaction solution after absorption is extracted using hexamethylene, 40 DEG C of extraction temperature, n-hexane and reaction solution quality
Than for 2:1, three times, the unreacted raw material contained in elimination reaction liquid makes monomer content lower than 0.5wt% for continuous extraction,
Obtain polyisocyanate product.
Through detecting, fluorine element content testing result in the polyisocyanate product that embodiment 2 obtains are as follows:
50ppm；The molar content of the molar content of imino group oxadiazines diketone group and isocyanurate group in product
The ratio between be 1.2,25 DEG C of product viscosities be 620cP.
Comparative example 2
Comparative example 2 compared with Example 2, in step b), directly by the reaction solution after termination at 60 DEG C, by two-stage
Polytetrafluoroethylene packing is adsorbed, and the partial size of above-mentioned polytetrafluoroethylene packing is 1.0mm；
Through detecting, fluorine element content testing result in the polyisocyanate product that comparative example 2 obtains are as follows: 120ppm；Product
The ratio between molar content and the molar content of isocyanurate group of middle imino group oxadiazines diketone group are 1.15,25 DEG C of viscosity
For 650cP.
Embodiment 3
A) 1000g pentamethylene diisocyanate is placed in equipped with reflux condensing tube, blender, thermometer and nitrogen inlet
Round-bottomed flask in, the n-hexyl alcohol solution 1g of 60wt% tetrabutyl ammonium fluoride is added after being heated to 60 DEG C, and under constant stirring
Self-polymeric reaction is carried out, controls reaction temperature between 60~65 DEG C；It is stood when the conversion ratio of monomer in self-polymeric reaction reaches 40%
The C with tetrabutyl ammonium fluoride equimolar amounts is added3F7CH2O(CH2CH2O)10H, reaction can be terminated by continuing stirring 15min；
B) reaction solution after termination is cooled to -30 DEG C, and passes through two-stage polytetrafluoroethylene (PTFE) sock filtration, above-mentioned poly- four
The aperture 70um of vinyl fluoride filter bag；
C) filtered reaction solution is evaporated under conditions of 150 DEG C of temperature, absolute pressure 100Pa using thin film evaporator
The unreacted raw material contained in elimination reaction liquid makes monomer content lower than 0.5wt%, obtains polyisocyanate product.
Through detecting, fluorine element content testing result in the polyisocyanate product that embodiment 3 obtains are as follows: 60ppm；In product
The ratio between molar content and the molar content of isocyanurate group of imino group oxadiazines diketone group are glued for 1.1,25 DEG C of products
Degree is 710cP.
Embodiment 4
Embodiment 4 compared with Example 3, unlike: select 0.5g 60wt% tetrabutyl fluoram n-hexyl alcohol it is molten
Liquid is as catalyst；
Through detecting, fluorine element content testing result in the polyisocyanate product that embodiment 4 obtains are as follows: 50ppm；Product
The ratio between molar content and the molar content of isocyanurate group of middle imino group oxadiazines diketone group are 1.08,25 DEG C of products
Viscosity is 720cP.
The said goods are placed in Aluminum Bottle and are stored in -18 DEG C of refrigerator, its phenomenon is observed, as a result such as table 1:
Product apparently changes when 1 low temperature of table stores
| Initially | After 1 month | After 2 months | After 3 months | |
| Embodiment 1 | Clarification | Clarification | Clarification | Clarification |
| Comparative example 1-1 | Clarification | Clarification | Clarification | It is muddy |
| Comparative example 1-2 | Clarification | Clarification | It is muddy | It is muddy |
| Comparative example 1-3 | Clarification | It is muddy | It is muddy | It is muddy |
| Embodiment 2 | Clarification | Clarification | Clarification | Clarification |
| Comparative example 2 | Clarification | Clarification | Clarification | It is muddy |
| Embodiment 3 | Clarification | Clarification | Clarification | Clarification |
| Embodiment 4 | Clarification | Clarification | Clarification | Clarification |
By data in upper table 1 it is found that the polyisocyanate product obtained using invention preparation method can be after 3 months
Clear state is still kept under low temperature, and there is good apparent property；The polyisocyanate product that comparative example 1-1, comparative example 2 obtain
Clear state can still be kept under low temperature after 2 months, but to there is turbid phenomenon after 3 months；Comparative example 1-2 is obtained more
There is turbid phenomenon under low temperature after 2 months in isocyanate products, have the apparent property of difference；The polyisocyanate that comparative example 1-3 is obtained
Cyanate product occurred as soon as turbid phenomenon under low temperature after 1 month, had very poor apparent property.
Claims (13)
1. a kind of method for preparing polyisocyanates, which is characterized in that by isocyanates under the catalysis of fluorinated catalyst into
Terminator termination reaction is added after the reaction was completed and obtains reaction solution for row self-polymeric reaction；Unreacted isocyanate-monomer is removed
After obtain polyisocyanates；
Fluorine content control in the polyisocyanates is not higher than 80ppm.
2. the method according to claim 1, wherein by terminate reaction after reaction solution be cooled to -30~30 DEG C,
And absorption or filtration treatment are carried out with fluorinated material.
3. method according to claim 1 or 2, which is characterized in that the terminator is fluorinated terminator.
4. according to the method described in claim 3, it is characterized in that, in obtained polyisocyanates, imino group oxadiazines two
The ratio between molar content and the molar content of isocyanurate group of ketone groups are 0.5~1.5.
5. according to the method described in claim 4, it is characterized in that, the fluorinated terminator has the structure such as following formula (I):
CnF2n+1(CH2)xO(CH2CH2O)mH formula (I)
Wherein, n is the integer of 1-10, preferably 2-6；
M is the integer of 1-15, preferably 3-8；
X is 0,1,2,3.
6. method according to claim 1-5, which is characterized in that the fluorinated catalyst has such as following formula
(II) structure:
Wherein, R1、R2、R3、R4It is same or different, separately it is selected from the C of linear chain or branched chain1~C15Alkyl, any substitution
C7~C15Aralkyl or the C that arbitrarily replaces6~C12Aryl；
Z is selected from N or P；
Y is selected from fluorine or polyfluoro ion, and the structure of the polyfluoro ion is (F (HF)n)-, wherein n be 1~10 integer.
7. method according to claim 1-6, which is characterized in that the quality based on the isocyanates, it is described
The dosage of fluorinated catalyst is 10~1000ppm；The molar ratio of the terminator and the fluorinated catalyst amount is 1:1
~2:1.
8. the method according to the description of claim 7 is characterized in that it is characterized in that, the fluorinated catalyst is with solution shape
Formula is added to reaction system, and the solvent in selected fluorinated catalyst solution is methanol, ethyl alcohol, isobutanol, hexanol, tertiary fourth
One of alcohol, 1,4-butanediol are a variety of；The concentration of the fluorinated catalyst solution be 10~90wt%, preferably 30~
80wt%.
9. according to the described in any item methods of claim 2-8, which is characterized in that the fluorinated material is solid-state fluorinated material
Material, preferably polytetrafluoroethylene material further preferably have such as following formula (III) structure:
[CF2-CF2]nFormula (III)
Wherein, n is 100~100000, preferably 200~5000, further preferably 500~3000；
Preferably, the mass content of fluorine is 50%~80% in the fluorinated material.
10. according to the method described in claim 9, it is characterized in that, the fluorinated material is polytetrafluoroethylene (PTFE) filter bag, poly- four
Vinyl fluoride filter core or polytetrafluoroethylene packing；
Preferably, the aperture of the polytetrafluoroethylene (PTFE) filter bag and polytetrafluoroethylene (PTFE) filter core is between 5~100um, preferably 10~
50um, the partial size of the polytetrafluoroethylene packing are 0.5~1.5mm.
11. -10 described in any item methods according to claim 1, which is characterized in that the isocyanates is C4~C20Fat
(cyclo) aliphatic diisocyanates, C4~C20Alicyclic diisocyanate and C6~C20One of aromatic diisocyanate or more
Kind；
Preferably, the isocyanates be hexamethylene diisocyanate, pentamethylene diisocyanate, methylpentane -1 2-,
5- diisocyanate, 1,3- bis- (isocyanatomethyl) hexamethylene, Isosorbide-5-Nitrae-two (isocyanatomethyl) hexamethylene, norborneol
Alkane dimethylene isocyanates, 2,2,4- trimethyl hexamethylene diisocyanates, 2,4,4- trimethyl hexamethylene diisocyanates and 4,4'- bis-
One of diphenylmethane diisocyanate is a variety of.
12. -11 described in any item methods according to claim 1, which is characterized in that guarantor of the self-polymeric reaction in inert gas
Under shield, carried out under conditions of temperature is 10~100 DEG C, the inert gas is preferably nitrogen and/or argon gas.
13. according to the method for claim 12, which is characterized in that select thin film evaporation, the mode of molecular distillation or extraction
Remove the unreacted isocyanate-monomer.
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| CN110540633A (en) * | 2019-09-12 | 2019-12-06 | 万华化学集团股份有限公司 | polyisocyanate composition and preparation method thereof |
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| CN111793182B (en) * | 2020-07-15 | 2022-04-22 | 万华化学集团股份有限公司 | Polyisocyanate composition |
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