CN106519184A - Preparing method of high polymer containing oxazolidinone ring - Google Patents
Preparing method of high polymer containing oxazolidinone ring Download PDFInfo
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- CN106519184A CN106519184A CN201610961246.4A CN201610961246A CN106519184A CN 106519184 A CN106519184 A CN 106519184A CN 201610961246 A CN201610961246 A CN 201610961246A CN 106519184 A CN106519184 A CN 106519184A
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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
- C08G18/06—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
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
- C08G18/8074—Lactams
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- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- 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
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/20—Heterocyclic amines; Salts thereof
- C08G18/2009—Heterocyclic amines; Salts thereof containing one heterocyclic ring
- C08G18/2027—Heterocyclic amines; Salts thereof containing one heterocyclic ring having two nitrogen atoms in the ring
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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
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
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- 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
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/8064—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds
- C08G18/8067—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds phenolic compounds
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- C—CHEMISTRY; METALLURGY
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- 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
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
- C08G18/8077—Oximes
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Abstract
The invention relates to a preparing method of a high polymer containing an oxazolidinone ring. The preparing method includes the steps that polyhydric alcohol and diisocyanate react in the presence of organic solvent to prepare an isocyanate-terminated prepolymer; in the presence of organic solvent remaining isocyanate groups in the isocyanate-terminated prepolymer are completed blocked to obtain an isocyanate blocked substance; the isocyanate blocked substance and aliphatic epoxy resin react in the presence of a catalyst, the high polymer containing the oxazolidinone ring is obtained through reduced pressure distillation after reaction is completed, wherein the molar ratio of additive amount of aliphatic epoxy resin to remaining isocyanate groups in the first step is (1.5-2.5):1. The oxazolidinone polymer is obtained through a three-step method, in the method, the reaction rate can be effectively controlled, and it is avoided that gel is generated in the product due to excessively intense reaction. The synthesized oxazolidinone polymer is good in performance, mild in viscosity and high in temperature resisting index and has important significance in researching H-level oxazolidinone solvent-free insulating paint.
Description
Technical field
Present invention relates particularly to a kind of preparation method of the high polymer of ring containing oxazolidone.
Background technology
In the equipment such as motor, electrical equipment, the ratio shared by insulant is very big.It is also link the weakest simultaneously, especially
Which is that, under conditions of high temperature, electrical equipment is easier aging and damages.Therefore, develop the high insulant of temperature classification for
The development of high efficiency motor is promoted to have great importance.
Polyoxazolidone resin is a kind of new insulant, up to 180 DEG C of its temperature classification.Report in document at present
Preparation method be typically one-step method be directly synthesized oxazolidone high polymer.However, due to the NCO in synthesis material
The activity of group is very high, and reaction rate is wayward, generally requires just be accomplished under the protection of a large amount of solvents, and then only
The insullac for having solvent can be obtained, certain harm is caused to ecological environment.
The structural formula of oxazolidone ring is：
Oxazolidone ring is the specific reactional equation by being obtained with di-isocyanate reaction containing bifunctional epoxy compound
Formula is as follows：
Isocyanate groups (- NCO) are a kind of highly undersaturated active groups.If epoxy resin is straight with diisocyanate
Connect and adopt polymerisation in bulk, reaction system will be easy to as reaction rate is wayward, in course of reaction, release substantial amounts of heat, and
Ultimately result in product and gel occurs.
The content of the invention
The technical problem to be solved is to provide a kind of preparation of the controllable high polymer of ring containing oxazolidone of reaction
Method.
To solve above technical problem, the present invention is adopted the following technical scheme that：
A kind of preparation method of the high polymer of ring containing oxazolidone, comprises the steps：
The first step, polyhydric alcohol and diisocyanate are reacted in presence of organic solvent prepare isocyanate terminated pre-polymerization
Thing；
Second step, in presence of organic solvent, will be remaining different in described ending isocyanate prepolymer with sealer
The completely enclosed prepared isocyanates closure of cyanate group；
3rd step, described isocyanates closure and aliphatic epoxy resin are carried out instead in the presence of a catalyst
Should, Jing vacuum distillations after reaction is completed obtain the described high polymer of ring containing oxazolidone, wherein, the addition of aliphatic epoxy resin
The molar ratio of amount and the remaining isocyanate groups of the first step is 1.5～2.5：1.
When the adding too much of aliphatic epoxy resin, the heat resistance of oxazolidone high polymer will be had a strong impact on.
In the present invention, the reaction equation of the first step is：
The reaction equation of second step is (by taking caprolactam as an example)：
Remaining isocyanate groups in ending isocyanate prepolymer are completely enclosed by sealer so as to lost at normal temperatures
Reactivity；
The reaction equation of the 3rd step is (by taking caprolactam as an example)：
There is deblocking reaction in isocyanates closure, discharge again active NCO at high temperature
Group, the isocyanate groups are reacted with aliphatic epoxy resin at high temperature.
Preferably, the diisocyanate in the first step is methyl diphenylene diisocyanate or toluene di-isocyanate(TDI).
Preferably, the polyhydric alcohol in the first step is Polyethylene Glycol, polyether polyol or trimethylolpropane.
Preferably, the organic solvent in the first step be ethyl acetate, toluene, one or more in cyclohexanone of combination.
Preferably, the molar ratio of the hydroxyl in the isocyanate groups and polyhydric alcohol in the diisocyanate in the first step
For 3.5～4.5:1, more preferably 4：1.
Preferably, the reaction condition of the first step is that temperature is maintained at 60～70 DEG C, sustained response under nitrogen atmosphere protection
4～6 hours.
Preferably, the quality that feeds intake of the organic solvent in the first step is that described diisocyanate feeds intake the 1～2.5 of quality
Times.
Preferably, the sealer in second step is methanol, phenol, ethanethio, methyl ethyl ketoxime, sodium sulfite, acetyl
Acetone, caprolactam, diethyl malonate, cyclohexanone-oxime, methylphenylamine, hydrocyanic acid or thionaphthol.
Preferably, the organic solvent in second step is toluene or ethyl acetate.
Preferably, after the sealer in second step is reacted with the first step, the mol ratio of remaining isocyanate groups is more than 1：
1, more preferably 1.2:1.
Preferably, the quality that feeds intake of the organic solvent in second step is that described sealer feeds intake 3～6 times of quality.
Preferably, the reaction condition of second step is that temperature is maintained at 50～70 DEG C, sustained response under nitrogen atmosphere protection
2～4 hours, till isocyanate groups substantially completely disappear.
Preferably, the catalyst in the 3rd step is 2-ethyl-4-methylimidazole.
Preferably, the quality that feeds intake of described catalyst is described isocyanates closure and described aliphatic epoxy
The 0.1%～0.5% of resin gross mass.
Preferably, the reaction condition of the 3rd step is that temperature is maintained at 150～160 DEG C under nitrogen atmosphere protection, is continued anti-
Answer 3～4 hours.
Due to the enforcement of above technical scheme, the present invention is had the advantage that compared with prior art：
1. the present invention synthesizes oxazolidon polymers using three-step approach, and the method can effectively control reaction rate, keep away
Exempt from product as reaction excessively acutely occurs gel.2. the present invention in synthesize oxazolidon polymers function admirable, viscosity
Moderate, heatproof index is higher, is of great significance to studying H level oxazolidones solvent-free insulated paint tool.3. have studied ring
Impact of the addition of oxygen tree fat to oxazolidone superpolymer performance, has guidance meaning to the synthesis technique of oxazolidone high polymer
Justice.
Description of the drawings
Accompanying drawing 1 is the infrared spectrogram of the synthesis oxazolidon polymers of the synthesis of embodiment 1.
Specific embodiment
With reference to specific embodiment, the present invention will be described in detail.Reaction condition in embodiment can basis
Specific to require to be adjusted accordingly, raw material used is all technical grade.
Embodiment 1
A kind of preparation method of the high polymer of ring containing oxazolidone, specific synthesis step are as follows：
The first step, weigh 57.5g (0.14mol, hydroxy radical content are 0.28mol) Polyethylene Glycol (PEG-400), 4～6 drop phosphorus
Acid is added in four-hole boiling flask, is warming up to 120 DEG C of vacuum distillations 4～6 hours (vacuum 0.1MPa), until in Polyethylene Glycol
Moisture be removed completely.100g (0.57mol, the content of isocyanate groups is 1.14mol) toluene diisocyanate is weighed afterwards
Acid esters (TDI), 200g ethyl acetates are added in the four-hole boiling flask equipped with agitator, condensing tube, thermometer and nitrogen shielding gas,
Then the Polyethylene Glycol after being dehydrated is slowly dropped in the flask under the conditions of 60～70 DEG C, sustained response 4～6 hours,
Prepare ending isocyanate prepolymer.After reaction, the content of remaining isocyanate groups is 0.86mol.
Second step, weigh 116.8g (1.032mol) caprolactam, 500g toluene be added to equipped with agitator, condensing tube,
In the four-hole boiling flask of thermometer and nitrogen shielding gas.Afterwards 357.5g ending isocyanate prepolymers prepared by the first step are slowly dripped
It is added in the four-hole boiling flask, is progressively warming up to 50～70 DEG C, sustained response 2～4 hours, until isocyanate groups are substantially completely
Till disappearance, isocyanates closure is prepared.The mass fraction of the isocyanate groups in closure adopts two positive fourth of acetone
Amine titrimetry carries out quantitative measurement.
3rd step, by 433.97g (1.72mol) 3,4- epoxy-cyclohexanes formic acid -3 ', 4 '-epoxy-cyclohexane methyl ester
(CY-179) the 974.3g isocyanates closure mixing that, prepared by 4.22g 2-ethyl-4-methylimidazoles (EMI) and second step is equal
Put into after even in the four-hole boiling flask equipped with agitator, condensing tube and nitrogen shielding gas, be progressively warming up to 150～160 DEG C of reactions 3
～4 hours, prepare the high polymer containing oxazolidone ring.After the completion of question response, the method distilled using vacuum decompression will have
Machine solvent is steamed from reaction system.
Embodiment 2
The first step, weigh 57.5g (0.14mol, hydroxy radical content are 0.28mol) Polyethylene Glycol (PEG-400), 4～6 drop phosphorus
Acid is added in four-hole boiling flask, is warming up to 120 DEG C of vacuum distillations 4～6 hours (vacuum 0.1MPa), until in Polyethylene Glycol
Moisture be removed completely.143.7g (0.57mol, the content of isocyanate groups is 1.14mol) diphenylmethyl is weighed afterwards
Alkane diisocyanate (MDI), 200g ethyl acetates are added to equipped with agitator, condensing tube, thermometer and nitrogen shielding gas four
In mouth flask, then the Polyethylene Glycol after being dehydrated is slowly dropped in the flask under the conditions of 60～70 DEG C, sustained response 4
～6 hours, prepare ending isocyanate prepolymer.After reaction, the content of remaining isocyanate groups is 0.86mol.
Second step, weigh 89.9g (1.032mol) methyl ethyl ketoxime, 500g ethyl acetates be added to equipped with agitator, condensation
In the four-hole boiling flask of pipe, thermometer and nitrogen shielding gas.Afterwards 401.2g ending isocyanate prepolymers prepared by the first step are delayed
Slowly it is added drop-wise in the four-hole boiling flask, is progressively warming up to 50～70 DEG C, sustained response 2～4 hours, until isocyanate groups are basic
Till being wholly absent, isocyanates closure is prepared.The mass fraction of the isocyanate groups in closure adopts acetone two
N-Butylamine titration method carries out quantitative measurement.
3rd step, by 433.97g (1.72mol) 3,4- epoxy-cyclohexanes formic acid -3 ', 4 '-epoxy-cyclohexane methyl ester
(CY-179) the 991.1g isocyanates closure mixing that, prepared by 4.28g 2-ethyl-4-methylimidazoles (EMI) and second step is equal
Put into after even in the four-hole boiling flask equipped with agitator, condensing tube and nitrogen shielding gas, be progressively warming up to 150～160 DEG C of reactions 3
～4 hours, prepare the high polymer containing oxazolidone ring.After the completion of question response, the method distilled using vacuum decompression will have
Machine solvent is steamed from reaction system.
Embodiment 3
The first step, weigh 100g (0.57mol, the content of isocyanate groups are 1.14mol) toluene di-isocyanate(TDI),
200g ethyl acetates are added in the four-hole boiling flask equipped with agitator, condensing tube, thermometer and nitrogen shielding gas；Weigh afterwards
12.5g (0.093mol, hydroxy radical content are 0.28mol) trimethylolpropane (TMP) is dissolved in 100g cyclohexanones, then will be solubilized
The trimethylolpropane (TMP) of solution is slowly dropped in four-hole boiling flask, after completion of dropping, reaction temperature is progressively warming up to 60
～70 DEG C, sustained response 4～6 hours prepares ending isocyanate prepolymer.The content of remaining isocyanate groups after reaction
For 0.86mol.
Second step, weigh 89.9g (1.032mol) methyl ethyl ketoxime, 500g ethyl acetates be added to equipped with agitator, condensation
In the four-hole boiling flask of pipe, thermometer and nitrogen shielding gas.Afterwards 412.5g ending isocyanate prepolymers prepared by the first step are delayed
Slowly it is added drop-wise in the four-hole boiling flask, is progressively warming up to 50～70 DEG C, sustained response 2～4 hours, until isocyanate groups are basic
Till being wholly absent, isocyanates closure is prepared.The mass fraction of the isocyanate groups in closure adopts acetone two
N-Butylamine titration method carries out quantitative measurement.
3rd step, by 433.97g (1.72mol) 3,4- epoxy-cyclohexanes formic acid -3 ', 4 '-epoxy-cyclohexane methyl ester
(CY-179) the 1002.4g isocyanates closure mixing that, prepared by 4.31g 2-ethyl-4-methylimidazoles (EMI) and second step
Put in the four-hole boiling flask equipped with agitator, condensing tube and nitrogen shielding gas after uniform, be progressively warming up to 150～160 DEG C instead
Answer 3～4 hours, prepare the high polymer containing oxazolidone ring.After the completion of question response, the method distilled using vacuum decompression will
Organic solvent is steamed from reaction system.
Embodiment 4
The first step, weigh 57.5g (0.14mol, hydroxy radical content are 0.28mol) Polyethylene Glycol (PEG-400), 4～6 drop phosphorus
Acid is added in four-hole boiling flask, is warming up to 120 DEG C of vacuum distillations 4～6 hours (vacuum 0.1MPa), until in Polyethylene Glycol
Moisture be removed completely.100g (0.57mol, the content of isocyanate groups is 1.14mol) toluene diisocyanate is weighed afterwards
In the four-hole boiling flask equipped with agitator, condensing tube, thermometer and nitrogen shielding gas, then acid esters, 200g ethyl acetates are added to
The Polyethylene Glycol after being dehydrated is slowly dropped in the flask under the conditions of 60～70 DEG C, sustained response 4～6 hours, is prepared
Go out ending isocyanate prepolymer.After reaction, the content of remaining isocyanate groups is 0.86mol.
Second step, weigh 97.1g (1.032mol) phenol, 500g toluene and be added to equipped with agitator, condensing tube, thermometer
In the four-hole boiling flask of nitrogen shielding gas.357.5g ending isocyanate prepolymers prepared by the first step are slowly dropped to into this afterwards
In four-hole boiling flask, 50～70 DEG C are progressively warming up to, sustained response 2～4 hours, until isocyanate groups substantially completely disappear and are
Only, prepare isocyanates closure.The mass fraction of the isocyanate groups in closure is titrated using acetone di-n-butylamine
Method carries out quantitative measurement.
3rd step, by 433.97g (1.72mol) 3,4- epoxy-cyclohexanes formic acid -3 ', 4 '-epoxy-cyclohexane methyl ester
(CY-179) the 954.6g isocyanates closure mixing that, prepared by 4.17g 2-ethyl-4-methylimidazoles (EMI) and second step is equal
Put into after even in the four-hole boiling flask equipped with agitator, condensing tube and nitrogen shielding gas, be progressively warming up to 150～160 DEG C of reactions 3
～4 hours, prepare the high polymer containing oxazolidone ring.After the completion of question response, the method distilled using vacuum decompression will have
Machine solvent is steamed from reaction system.
Embodiment 5
The first step, to weigh 143.7g (0.57mol, the content of isocyanate groups are 1.14mol) diphenyl methane two different
Cyanate (MDI), 200g ethyl acetates are added to the four-hole boiling flask equipped with agitator, condensing tube, thermometer and nitrogen shielding gas
In, 12.5g (0.093mol, hydroxy radical content are 0.28mol) trimethylolpropane (TMP) is weighed afterwards is dissolved in 100g cyclohexanones
In, then the trimethylolpropane for having dissolved (TMP) is slowly dropped in four-hole boiling flask, after completion of dropping, will reaction temperature
Degree is progressively warming up to 60～70 DEG C, and sustained response 4～6 hours prepares ending isocyanate prepolymer.Remaining isocyanide after reaction
The content of acid esters group is 0.86mol.
Second step, weigh 116.8g (1.032mol) caprolactam, 500g toluene be added to equipped with agitator, condensing tube,
In the four-hole boiling flask of thermometer and nitrogen shielding gas.Afterwards 456.2g ending isocyanate prepolymers prepared by the first step are delayed
Slowly it is added drop-wise in the four-hole boiling flask, is progressively warming up to 50～70 DEG C, sustained response 2～4 hours, until isocyanate groups are basic
Till being wholly absent, isocyanates closure is prepared.The mass fraction of the isocyanate groups in closure adopts acetone two
N-Butylamine titration method carries out quantitative measurement.
3rd step, by 433.97g (1.72mol) 3,4- epoxy-cyclohexanes formic acid -3 ', 4 '-epoxy-cyclohexane methyl ester
(CY-179) the 1073g isocyanates closure mixing that, prepared by 4.52g 2-ethyl-4-methylimidazoles (EMI) and second step is equal
Put into after even in the four-hole boiling flask equipped with agitator, condensing tube and nitrogen shielding gas, be progressively warming up to 150～160 DEG C of reactions 3
～4 hours, prepare the high polymer containing oxazolidone ring.After the completion of question response, the method distilled using vacuum decompression will have
Machine solvent is steamed from reaction system.
Comparative example 1 (one-step synthesis method oxazolidone high polymer)
Weigh 143.7g (0.57mol) methyl diphenylene diisocyanate (MDI), 215.7g (0.855mol) 3,4- epoxies
Butylcyclohexanecarboxylic acid -3 ', 4 '-epoxy-cyclohexane methyl ester (CY-179), 200g ethyl acetates and 1.68g 2- ethyl -4- methyl
Imidazoles (EMI) is added in the four-hole boiling flask equipped with agitator, condensing tube, thermometer and nitrogen shielding gas, is progressively warming up to 150
～160 DEG C are reacted.Experimental result finds：Reaction is acutely carried out, and gel occurs quickly.The experiment is demonstrated by one-step method
When being directly synthesized oxazolidone high polymer, reaction rate is wayward, is susceptible to gel and leads to not synthesize oxazolidone
High polymer.
Comparative example 2 (epoxy resin selects the bisphenol A type epoxy resin that viscosity is big, molecular weight is high)
The first step, weigh 57.5g (0.14mol, hydroxy radical content are 0.28mol) Polyethylene Glycol (PEG-400), 4～6 drop phosphorus
Acid is added in four-hole boiling flask, is warming up to 120 DEG C of vacuum distillations 4～6 hours (vacuum 0.1MPa), until in Polyethylene Glycol
Moisture be removed completely.100g (0.57mol, the content of isocyanate groups is 1.14mol) toluene diisocyanate is weighed afterwards
Acid esters (TDI), 200g ethyl acetates are added in the four-hole boiling flask equipped with agitator, condensing tube, thermometer and nitrogen shielding gas,
Then the Polyethylene Glycol after being dehydrated is slowly dropped in the flask under the conditions of 60～70 DEG C, sustained response 4～6 hours,
Prepare ending isocyanate prepolymer.After reaction, the content of remaining isocyanate groups is 0.86mol.
Second step, weigh 116.8g (1.032mol) caprolactam, 500g toluene be added to equipped with agitator, condensing tube,
In the four-hole boiling flask of thermometer and nitrogen shielding gas.Afterwards 357.5g ending isocyanate prepolymers prepared by the first step are slowly dripped
It is added in the four-hole boiling flask, is progressively warming up to 50～70 DEG C, sustained response 2～4 hours, until isocyanate groups are substantially completely
Till disappearance, isocyanates closure is prepared.The mass fraction of the isocyanate groups in closure adopts two positive fourth of acetone
Amine titrimetry carries out quantitative measurement.
3rd step, by 390.9g (1.72mol) bisphenol A type epoxy resin, (6101 epoxy resin, epoxide number are 4.4mol/
Kg), after 974.3g isocyanates closure mix homogeneously prepared by 4.09g 2-ethyl-4-methylimidazoles (EMI) and second step
Put in the four-hole boiling flask equipped with agitator, condensing tube and nitrogen shielding gas, be progressively warming up to 150～160 DEG C and reacted.
Experimental result finds：Substantial amounts of heat is released in course of reaction, and product occurs gel quickly.The experiment shows：In synthesis azoles
It is during alkanone high polymer, also critically important for the selection of epoxy resin.In order to synthesize low viscous oxazolidone high polymer,
Should choose that molecular weight is relatively low, the less epoxy resin of viscosity.
(molar ratio of the remaining isocyanate groups of addition and the first step of aliphatic epoxy resin is for comparative example 3
4：1)
The first step, weigh 57.5g (0.14mol, hydroxy radical content are 0.28mol) Polyethylene Glycol (PEG-400), 4～6 drop phosphorus
Acid is added in four-hole boiling flask, is warming up to 120 DEG C of vacuum distillations 4～6 hours (vacuum 0.1MPa), until in Polyethylene Glycol
Moisture be removed completely.100g (0.57mol, the content of isocyanate groups is 1.14mol) toluene diisocyanate is weighed afterwards
Acid esters (TDI), 200g ethyl acetates are added in the four-hole boiling flask equipped with agitator, condensing tube, thermometer and nitrogen shielding gas,
Then the Polyethylene Glycol after being dehydrated is slowly dropped in the flask under the conditions of 60～70 DEG C, sustained response 4～6 hours,
Prepare ending isocyanate prepolymer.After reaction, the content of remaining isocyanate groups is 0.86mol.
Second step, weigh 116.8g (1.032mol) caprolactam, 500g toluene be added to equipped with agitator, condensing tube,
In the four-hole boiling flask of thermometer and nitrogen shielding gas.Afterwards 357.5g ending isocyanate prepolymers prepared by the first step are slowly dripped
It is added in the four-hole boiling flask, is progressively warming up to 50～70 DEG C, sustained response 2～4 hours, until isocyanate groups are substantially completely
Till disappearance, isocyanates closure is prepared.The mass fraction of the isocyanate groups in closure adopts two positive fourth of acetone
Amine titrimetry carries out quantitative measurement.
3rd step, by 867.9g (3.44mol) 3,4- epoxy-cyclohexanes formic acid -3 ', 4 '-epoxy-cyclohexane methyl ester
(CY-179) the 974.3g isocyanates closure mixing that, prepared by 5.53g 2-ethyl-4-methylimidazoles (EMI) and second step is equal
Put into after even in the four-hole boiling flask equipped with agitator, condensing tube and nitrogen shielding gas, be progressively warming up to 150～160 DEG C of reactions 3
～4 hours, prepare the high polymer containing oxazolidone ring.After the completion of question response, the method distilled using vacuum decompression will have
Machine solvent is steamed from reaction system.
(molar ratio of the remaining isocyanate groups of addition and the first step of aliphatic epoxy resin is for comparative example 4
6：1)
The first step, weigh 57.5g (0.14mol, hydroxy radical content are 0.28mol) Polyethylene Glycol (PEG-400), 4～6 drop phosphorus
Acid is added in four-hole boiling flask, is warming up to 120 DEG C of vacuum distillations 4～6 hours (vacuum 0.1MPa), until in Polyethylene Glycol
Moisture be removed completely.100g (0.57mol, the content of isocyanate groups is 1.14mol) toluene diisocyanate is weighed afterwards
Acid esters (TDI), 200g ethyl acetates are added in the four-hole boiling flask equipped with agitator, condensing tube, thermometer and nitrogen shielding gas,
Then the Polyethylene Glycol after being dehydrated is slowly dropped in the flask under the conditions of 60～70 DEG C, sustained response 4～6 hours,
Prepare ending isocyanate prepolymer.After reaction, the content of remaining isocyanate groups is 0.86mol.
Second step, weigh 116.8g (1.032mol) caprolactam, 500g toluene be added to equipped with agitator, condensing tube,
In the four-hole boiling flask of thermometer and nitrogen shielding gas.Afterwards 357.5g ending isocyanate prepolymers prepared by the first step are slowly dripped
It is added in the four-hole boiling flask, is progressively warming up to 50～70 DEG C, sustained response 2～4 hours, until isocyanate groups are substantially completely
Till disappearance, isocyanates closure is prepared.The mass fraction of the isocyanate groups in closure adopts two positive fourth of acetone
Amine titrimetry carries out quantitative measurement.
3rd step, by 1301.9g (5.16mol) 3,4- epoxy-cyclohexanes formic acid -3 ', 4 '-epoxy-cyclohexane methyl ester
(CY-179) the 974.3g isocyanates closure mixing that, prepared by 6.83g 2-ethyl-4-methylimidazoles (EMI) and second step is equal
Put into after even in the four-hole boiling flask equipped with agitator, condensing tube and nitrogen shielding gas, be progressively warming up to 150～160 DEG C of reactions 3
～4 hours, prepare the high polymer containing oxazolidone ring.After the completion of question response, the method distilled using vacuum decompression will have
Machine solvent is steamed from reaction system.
The Specifeca tion speeification of the oxazolidon polymers synthesized in the present invention is shown in Table 1.Wherein existed using rotational viscometer
The viscosity of oxazolidon polymers is determined at 25 DEG C；The heatproof index of oxazolidone solidfied material is determined using thermogravimetry.Azoles
The preparation method of alkanone solidfied material is to add the methyl tetrahydro phthalic anhydride solidification of respective amount according to the content of hydroxyl unnecessary in system
Agent (MeTHPA), after mix homogeneously is placed in sample in the aluminum box of 45mm × 45mm × 20mm, is then placed in baking oven by 100 DEG C
Solidification solidifies 4 hours for 2 hours, 160 DEG C, 200 DEG C of solidifications programs of 2 hours are solidified.
Table 1
| Performance indications | Outward appearance | Viscosity (mPa.S) | Heatproof index (DEG C) |
| Embodiment 1 | Rufous viscous liquid | 13953 | 196 |
| Embodiment 2 | Rufous viscous liquid | 15267 | 207 |
| Embodiment 3 | Rufous viscous liquid | 17541 | 195 |
| Embodiment 4 | Rufous viscous liquid | 14391 | 198 |
| Embodiment 5 | Rufous viscous liquid | 12496 | 203 |
| Comparative example 1 | Gel | - | - |
| Comparative example 2 | Gel | - | - |
| Comparative example 3 | Rufous viscous liquid | 10946 | 163 |
| Comparative example 4 | Rufous viscous liquid | 9869 | 145 |
Can draw the following conclusions from above table：When being 1. directly synthesized oxazolidone high polymer by one-step method, instead
Answer speed wayward, be susceptible to gel and lead to not synthesize oxazolidone high polymer.Three-step approach is taken to close in the present invention
Into oxazolidone high polymer, the synthetic method can effectively control reaction rate.2. in the mistake of synthesis oxazolidone high polymer
Cheng Zhong, it is also critically important for the selection of epoxy resin.In order to synthesize low viscous oxazolidone high polymer, molecular weight should be chosen
The less epoxy resin of relatively low, viscosity.3. when the addition of epoxy resin is larger, although oxazolidone high polymer can be reduced
Viscosity, but the heatproof index of oxazolidone high polymer is greatly reduced.
Fig. 1 is the infrared spectrogram of the oxazolidon polymers synthesized in the present invention.With reference to shown in Fig. 1, in wavelength it is
1755cm-1And 1720cm-1There is strong absworption peak at place, and the absworption peak is the characteristic peak of ester group in oxazolidone ring, illustrates azoles
Alkanone polymer is successfully synthesized.
Above the present invention is described in detail, its object is to allow the personage for being familiar with this art to will appreciate that this
The content of invention is simultaneously carried out, and can not be limited the scope of the invention with this, all spirit institutes of the invention
The equivalence changes of work or modification, should all cover within the scope of the present invention.
Claims (10)
1. a kind of preparation method of the high polymer of ring containing oxazolidone, it is characterised in that comprise the steps：
The first step, by polyhydric alcohol and diisocyanate, reaction prepares ending isocyanate prepolymer in presence of organic solvent；
Second step, in presence of organic solvent, with sealer by remaining Carbimide. in described ending isocyanate prepolymer
The completely enclosed prepared isocyanates closure of ester group；
3rd step, described isocyanates closure and aliphatic epoxy resin are reacted in the presence of a catalyst, instead
Jing vacuum distillations after should completing obtain the described high polymer of ring containing oxazolidone, wherein, the addition of aliphatic epoxy resin and
The mol ratio of the remaining isocyanate groups of the first step is 1.5 ~ 2.5：1.
2. the preparation method of the high polymer of ring containing oxazolidone according to claim 1, it is characterised in that：In the first step two
Isocyanates are methyl diphenylene diisocyanate or toluene di-isocyanate(TDI)；Polyhydric alcohol in the first step be Polyethylene Glycol,
Polyether polyol or trimethylolpropane；Organic solvent in the first step is ethyl acetate, toluene, the one kind in cyclohexanone or
Various combinations.
3. the preparation method of the high polymer of ring containing oxazolidone according to claim 1, it is characterised in that：In the first step two
The molar ratio of the hydroxyl in isocyanate groups and polyhydric alcohol in isocyanates is 3.5 ~ 4.5:1.
4. the preparation method of the high polymer of ring containing oxazolidone according to claim 1, it is characterised in that：The reaction of the first step
Condition is that temperature is maintained at 60 ~ 70 DEG C, sustained response 4 ~ 6 hours under nitrogen atmosphere protection.
5. the preparation method of the high polymer of ring containing oxazolidone according to claim 1, it is characterised in that：Having in the first step
The quality that feeds intake of machine solvent is that described diisocyanate feeds intake 1 ~ 2.5 times of quality.
6. the preparation method of the high polymer of ring containing oxazolidone according to claim 1, it is characterised in that：Envelope in second step
Close agent for methanol, phenol, ethanethio, methyl ethyl ketoxime, sodium sulfite, acetylacetone,2,4-pentanedione, caprolactam, diethyl malonate,
Cyclohexanone-oxime, methylphenylamine, hydrocyanic acid or thionaphthol；Organic solvent in second step is toluene or ethyl acetate.
7. the preparation method of the high polymer of ring containing oxazolidone according to claim 1, it is characterised in that：Preferably, second
After sealer and first step reaction in step, the mol ratio of remaining isocyanate groups is more than 1：1；It is organic molten in second step
The quality that feeds intake of agent is that described sealer feeds intake 3 ~ 6 times of quality.
8. the preparation method of the high polymer of ring containing oxazolidone according to claim 1, it is characterised in that：Second step it is anti-
Condition is answered to be that temperature is maintained at 50 ~ 70 DEG C, sustained response 2 ~ 4 hours under nitrogen atmosphere protection, until isocyanate groups
Till substantially completely disappearing.
9. the preparation method of the high polymer of ring containing oxazolidone according to claim 1, it is characterised in that：In 3rd step
Catalyst is 2-ethyl-4-methylimidazole, and the quality that feeds intake of described catalyst is described isocyanates closure and described
Aliphatic epoxy resin gross mass 0.1% ~ 0.5%.
10. the preparation method of the high polymer of ring containing oxazolidone according to claim 1, it is characterised in that：3rd step it is anti-
Condition is answered to be that temperature is maintained at 150 ~ 160 DEG C, sustained response 3 ~ 4 hours under nitrogen atmosphere protection.
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| CN110144035A (en) * | 2019-05-24 | 2019-08-20 | 桂林电子科技大学 | A kind of polyethylene glycol grafted epoxy resin composite material and preparation method thereof |
| CN112424253A (en) * | 2018-07-18 | 2021-02-26 | 巴斯夫欧洲公司 | Bulk polymerization of polyoxazolidinones |
| CN115490828A (en) * | 2022-11-02 | 2022-12-20 | 广州市嵩达新材料科技有限公司 | Modified polyoxazolidone prepolymer and high-temperature-resistant photocuring adhesive based on same |
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| CN115490828A (en) * | 2022-11-02 | 2022-12-20 | 广州市嵩达新材料科技有限公司 | Modified polyoxazolidone prepolymer and high-temperature-resistant photocuring adhesive based on same |
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