CN103012306A - Biology base molindone polyhydric alcohol as well as preparation method and application of biology base molindone polyhydric alcohol - Google Patents
Biology base molindone polyhydric alcohol as well as preparation method and application of biology base molindone polyhydric alcohol Download PDFInfo
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- CN103012306A CN103012306A CN2013100047484A CN201310004748A CN103012306A CN 103012306 A CN103012306 A CN 103012306A CN 2013100047484 A CN2013100047484 A CN 2013100047484A CN 201310004748 A CN201310004748 A CN 201310004748A CN 103012306 A CN103012306 A CN 103012306A
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- 0 *C(CN(CC(O1)I)C(CCCCN)C1=O)O Chemical compound *C(CN(CC(O1)I)C(CCCCN)C1=O)O 0.000 description 2
- NPOBLHSEVMIJIY-UHFFFAOYSA-N OCCN(CCO)C(CCCCN1)C1=O Chemical compound OCCN(CCO)C(CCCCN1)C1=O NPOBLHSEVMIJIY-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses biology base molindone polyhydric alcohol shown in a general formula (I). In the formula (I), R1 is H or CH3, and R2 is H or CH3. The invention also discloses a preparation method and application of the biology base molindone polyhydric alcohol. The biology base molindone polyhydric alcohol is prepared through reaction of 2-amino caprolactam and alkyleneoxide. The polyol prepared by adopting the method can be used for preparing rigid polyurethane foam.
Description
Technical field
The invention belongs to technical field of organic synthesis, be specifically related to class bio-based morpholone mai polyvalent alcohol and its preparation method and application.
Background technology
The characteristics such as rigid foam is little because of its density, intensity large, good weatherability, energy-conserving and environment-protective are widely applied in the every field of national economy, and rigid urethane foam (RPUF) is exactly outstanding person wherein.RPUF refers to not occur obvious deformation under the certain load effect, after the excessive generation deformation of load, can not return to the urethane foam of original state, have good physical and mechanical property, acoustical behavior, electric property and chemical resistance, the thermal conductivity that You Yiqi is extremely low is outstanding feature, is present optimal thermal insulation material.It can directly become polymer product from the raw material monomer time processing, can obtain by modes such as feed change chemical structure, specification, kinds the terminal goods of various performances and purposes, is widely used in being incubated the fields such as industry, packaging industry, shipbuilding industry.
Current, the mankind more and more pay close attention to environment, wish simultaneously to reduce the dependency to oil, and green, environmental protection, economy, gentle polyvalent alcohol are developed, and have become the important directions that polyvalent alcohol is developed.Based on this, people carry out the development research of related products with the natural resources of chemical research directional steering reproducible utilization.Prepare in the research of polyurethane material and the application and development at biopolyol at present both at home and abroad and also obtained some successful precedents, the soybean oil polyvalent alcohol in succession occurs, plam oil polyvalent alcohol, rapeseed oil polyvalent alcohol, the vegetable oil polyols such as castor oil polyhydric alcohol.According to patent US7977450B2 and WO2005/123669A1, the amino hexanolactam of 2-can directly be prepared by biofermentation products Methionin, utilizes the amino acid derivative of bio-based to prepare polyvalent alcohol, still finds no the successful report of research and development.
As making one of main component of urethane foam, polyvalent alcohol has tremendous influence to the performance of foam article.Introduce the poly-hydroxy structure by amino, can increase functionality, and technique is simple, purification step is simple, less energy consumption, and atom utilization is high, meets the principle of Green Chemistry " Atom economy ", and solvent is recyclable, produces without " three wastes ".In addition, in polyvalent alcohol, introduce hardness and the thermotolerance that the annular rigid structure can improve synthetic materials.
Summary of the invention
Technical problem to be solved by this invention provides a class bio-based morpholone mai polyvalent alcohol, hydroxyalkylation reaction introducing hydroxyl occurs in the amino at the amino hexanolactam of 2-, then the hydroxyalkylation reaction can occur and introduce hydroxyl, the preparation polyvalent alcohol in free another amino again.
The technical problem that the present invention also will solve provides the preparation technology of above-mentioned bio-based morpholone mai polyvalent alcohol.
The technical problem that the present invention will solve at last provides the application of above-mentioned bio-based morpholone mai polyvalent alcohol.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
A kind of bio-based morpholone mai polyvalent alcohol that is represented by following logical formula I:
Wherein,
R
1Be H or CH
3
R
2Be H or CH
3
The preparation method of above-mentioned bio-based morpholone mai polyvalent alcohol, in two kinds of situation.
Situation one: work as R
1Be different from R
2The time, adopt following 3 steps synthetic:
(1) the amino hexanolactam of 2-and epoxy alkane reaction obtain compound (II);
Wherein, R
1Be H or CH
3
(2) compound (II) that step (1) is obtained prepares compound (III) under heating condition;
Wherein, R
1Be H or CH
3
(3) compound (III) that step (2) is obtained obtains bio-based morpholone mai polyvalent alcohol with the epoxy alkane reaction;
Wherein, R
1Be H or CH
3, R
2Be H or CH
3, R
1Be different from R
2
Situation two is worked as R
1With R
2When identical, adopt single stage method synthetic, step is as follows:
(4) the amino hexanolactam of 2-and oxyethane or propylene oxide reaction obtain bio-based morpholone mai polyvalent alcohol;
In the step (1), the mol ratio of the amino hexanolactam of 2-and epoxy alkane is 1:2～3, and reaction solvent is methyl alcohol, and temperature of reaction is controlled at 20～80 ℃, and the reaction times is 2～24 hours.
In the step (2), described heating condition is 20 ℃～80 ℃, and reaction solvent is methyl alcohol, 2～24 hours reaction times.
In the step (3), compound (III) is 1:2～3 with the mol ratio of epoxy alkane, and reaction solvent is methyl alcohol, and temperature of reaction is controlled at 20 ℃～80 ℃, and the reaction times is 2～24 hours.
In the step (4), the mol ratio of the amino hexanolactam of 2-and oxyethane or propylene oxide is 1:4～6, and reaction solvent is methyl alcohol, and temperature of reaction is controlled at 20 ℃～80 ℃, and the reaction times is 2～24 hours.
The application of above-mentioned bio-based morpholone mai polyvalent alcohol in the preparation hard polyurethane foam.
Beneficial effect: the present invention has the functionality controllability strong take the amino hexanolactam of lysine derivative 2-as the polyvalent alcohol that raw material prepares, narrow molecular weight distribution, and reactive behavior is high, can prepare easily the characteristics of the product of high functionality.In addition, in polyvalent alcohol, introduce hardness and the thermotolerance that the annular rigid structure can improve synthetic materials.
Embodiment
According to following embodiment, the present invention may be better understood.Yet, those skilled in the art will readily understand, the described content of embodiment only is used for explanation the present invention, and should also can not limit the present invention described in detail in claims.
Embodiment 1:N, the preparation of the amino hexanolactam of N-two (2-hydroxyethyl)-2-.
To add 2-amino hexanolactam 25.6g (0.2mol), methyl alcohol 300ml in the sealed reactor of 500ml, stirring and dissolving passes into oxyethane 17.6g (0.4mol), continues to stir, and room temperature reaction is 3 hours again.Reacted with the method for underpressure distillation and removed methyl alcohol and remaining oxyethane, vacuum-drying 8～10 hours finally obtains N, the amino hexanolactam 43.3g of N-two (2-hydroxyethyl)-2-.ESI-MS?m/z:(M+H)=217.2。
Embodiment 2:N, the preparation of the amino hexanolactam of N-two (2-hydroxypropyl)-2-.
To add 2-amino hexanolactam 25.6g (0.2mol), methyl alcohol 300ml in the sealed reactor of 500ml, stirring and dissolving drips propylene oxide 34.8g (0.6mol), continues to stir, 60 ℃ of reactions 18 hours.Reacted with the method for underpressure distillation and removed methyl alcohol and remaining propylene oxide, vacuum-drying 8～10 hours finally obtains N, the amino hexanolactam 48.6g of N-two (2-hydroxypropyl)-2-.ESI-MS?m/z:(M+H)=245.2。
Embodiment 3:3-(4-aminobutyl)-4-(2-hydroxypropyl)-preparation of 6-methylmorpholine-2-ketone.
Add N in the sealed reactor with 500ml, the N-(2-hydroxypropyl)-2-amino hexanolactam 48.6g (0.2mol), methyl alcohol 300ml, stirring and dissolving, 80 ℃ were reacted 4 hours.Reacted with the method for underpressure distillation and removed methyl alcohol, vacuum-drying 8～10 hours finally obtains 3-(4-aminobutyl)-4-(2-hydroxypropyl)-6-methylmorpholine-2-ketone 48.7g.ESI-MSm/z:(M+H)=245.2。
Embodiment 4:3-(4-aminobutyl)-4-(2-hydroxyethyl) preparation of morpholine-2-ketone.
Add N in the sealed reactor with 500ml, N-two (2-hydroxyethyl)-2-amino hexanolactam 43.3g (0.2mol), methyl alcohol 300ml, stirring and dissolving, 20 ℃ were reacted 24 hours.Reacted with the method for underpressure distillation and removed methyl alcohol, vacuum-drying 8～10 hours finally obtains 3-(4-aminobutyl)-4-(2-hydroxyethyl) morpholine-2-ketone 43.3g.ESI-MSm/z:(M+H)=217.2。
Embodiment 5:3-{4-[two (2-hydroxyethyl) amino] butyl }-the 4-(2-hydroxypropyl)-preparation of 6-methylmorpholine-2-ketone.
Add 3-(4-aminobutyl)-4-(2-hydroxypropyl in the sealed reactor with 500ml)-6-methylmorpholine-2-ketone 48.7g (0.2mol), methyl alcohol 300ml, stirring and dissolving, pass into oxyethane 22g (0.5mol), continue to stir, 30 ℃ of reactions 4 hours.Reacted with the method for underpressure distillation and removed methyl alcohol and remaining oxyethane, vacuum-drying 8～10 hours finally obtains 3-{4-[two (2-hydroxyethyl) amino] butyl }-the 4-(2-hydroxypropyl)-6-methylmorpholine-2-ketone 66.5g.ESI-MS?m/z:(M+H)=333.2。
Embodiment 6:3-{4-[two (2-hydroxypropyl) amino] butyl }-the 4-(2-hydroxyethyl) preparation of morpholine-2-ketone.
Add 3-(4-aminobutyl)-4-(2-hydroxyethyl in the sealed reactor with 500ml)-6-methylmorpholine-2-ketone 43.3g (0.2mol), methyl alcohol 300ml, stirring and dissolving, drip propylene oxide 27.9g (0.48mol), continue to stir, 55 ℃ of reactions 16 hours.Reacted with the method for underpressure distillation and removed methyl alcohol and remaining propylene oxide, vacuum-drying 8～10 hours finally obtains 3-{4-[two (2-hydroxypropyl) amino] butyl }-the 4-(2-hydroxyethyl) morpholine-2-ketone 66.6g.ESI-MSm/z:(M+H)=333.2。
Embodiment 7:3-{4-[two (2-hydroxypropyl) amino] butyl }-the 4-(2-hydroxypropyl)-preparation of 6-methylmorpholine-2-ketone.
Will be in the sealed reactor of 500ml add 2-amino hexanolactam 25.6g (0.2mol), methyl alcohol 300ml, stirring and dissolving drips propylene oxide 46.4g (0.8mol), continues to stir, and 50 ℃ of reactions are 20 hours again.Reacted with the method for underpressure distillation and removed methyl alcohol and remaining propylene oxide, vacuum-drying 8～10 hours finally obtains 3-{4-[two (2-hydroxypropyl) amino] butyl }-the 4-(2-hydroxypropyl)-6-methylmorpholine-2-ketone 72.2g.ESI-MS?m/z:(M+H)=361.3。
Embodiment 8:3-{4-[two (2-hydroxyethyl) amino] butyl }-the 4-(2-hydroxyethyl) preparation of morpholine-2-ketone.
To add 2-amino hexanolactam 25.6g (0.2mol), methyl alcohol 300ml in the sealed reactor of 500ml, stirring and dissolving passes into oxyethane 52.8g (12mol), continues to stir, and 30 ℃ were reacted 2 hours.Reacted with the method for underpressure distillation and removed methyl alcohol and remaining oxyethane, vacuum-drying 8～10 hours finally obtains 3-{4-[two (2-hydroxyethyl) amino] butyl }-4-(2-hydroxyethyl) morpholine-2-ketone 61.0g.ESI-MS?m/z:(M+H
+)=305.2。
Embodiment 9: the performance test that the bio-based morpholone mai polyvalent alcohol of above-described embodiment 5～8 gained prepares hard polyurethane foam.
The present invention is as follows to the measuring method of the hard polyurethane foam of new bio polylol preparation:
(1) measures the apparent density of porous plastics according to GB/T 6343-1995;
(2) according to the compressive strength of GB/T 8813-88 mensuration rigid foam, getting foaming vertical direction cross section is compressing surface, and compression speed is 5mm/min, and the test value during sample thief 10% deflection is as the compressive strength of material.
Get the bio-based morpholone mai polyvalent alcohol 14g for preparing in above-described embodiment, with 4g polyether glycol 635(hydroxyl value 490mgKOH/g, the red Pola in Nanjing), 0.5g suds-stabilizing agent AK8803(Nanjing Mei Side), 0.1g hexahydroaniline (great river, Jiangdu chemical industry), 28g isocyanic ester PM200(Yantai ten thousand China), 7g blowing agent H CFC-141b(Changshu three likes rich fluorine chemical) reaction foams, can prepare hard polyurethane foams, density of material is between 30～43kg/m
3Between, vertical compression intensity is between 120～160KPa.
Table 1
Concrete data see Table 1.
Claims (7)
1. bio-based morpholone mai polyvalent alcohol that is represented by following logical formula I:
Wherein,
R
1Be H or CH
3
R
2Be H or CH
3
2. the preparation method of bio-based morpholone mai polyvalent alcohol claimed in claim 1 is characterized in that,
Work as R
1Be different from R
2The time, adopt following 3 steps synthetic:
(1) the amino hexanolactam of 2-and epoxy alkane reaction obtain compound (II);
Wherein, R
1Be H or CH
3
(2) compound (II) that step (1) is obtained prepares compound (III) under heating condition;
Wherein, R
1Be H or CH
3
(3) compound (III) that step (2) is obtained obtains bio-based morpholone mai polyvalent alcohol with the epoxy alkane reaction;
Wherein, R
1Be H or CH
3, R
2Be H or CH
3, R
1Be different from R
2
Work as R
1With R
2When identical, adopt single stage method synthetic, step is as follows:
(4) the amino hexanolactam of 2-and oxyethane or propylene oxide reaction obtain bio-based morpholone mai polyvalent alcohol;
3. the preparation method of bio-based morpholone mai polyvalent alcohol according to claim 2 is characterized in that, in the step (1), the mol ratio of the amino hexanolactam of 2-and epoxy alkane is 1:2～3, reaction solvent is methyl alcohol, and temperature of reaction is controlled at 20～80 ℃, and the reaction times is 2～24 hours.
4. the preparation method of bio-based morpholone mai polyvalent alcohol according to claim 2 is characterized in that, in the step (2), described heating condition is 20 ℃～80 ℃, and reaction solvent is methyl alcohol, 2～24 hours reaction times.
5. the preparation method of bio-based morpholone mai polyvalent alcohol according to claim 2 is characterized in that, in the step (3), compound (III) is 1:2～3 with the mol ratio of epoxy alkane, reaction solvent is methyl alcohol, and temperature of reaction is controlled at 20 ℃～80 ℃, and the reaction times is 2～24 hours.
6. the preparation method of bio-based morpholone mai polyvalent alcohol according to claim 2, it is characterized in that, in the step (4), the mol ratio of the amino hexanolactam of 2-and oxyethane or propylene oxide is 1:4～6, reaction solvent is methyl alcohol, temperature of reaction is controlled at 20 ℃～80 ℃, and the reaction times is 2～24 hours.
7. the application of bio-based morpholone mai polyvalent alcohol claimed in claim 1 in the preparation hard polyurethane foam.
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|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109912769A (en) * | 2019-02-18 | 2019-06-21 | 合肥科天水性科技有限责任公司 | A kind of polyalcohol modified aqueous polyurethane of biology base morpholone and its preparation method and application |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109912769A (en) * | 2019-02-18 | 2019-06-21 | 合肥科天水性科技有限责任公司 | A kind of polyalcohol modified aqueous polyurethane of biology base morpholone and its preparation method and application |
| CN109912769B (en) * | 2019-02-18 | 2021-07-13 | 合肥科天水性科技有限责任公司 | Bio-based morpholinone polyol modified waterborne polyurethane and preparation method and application thereof |
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