CN106242954B - The preparation method of polyetheramine low molecular polyether polyalcohol - Google Patents
The preparation method of polyetheramine low molecular polyether polyalcohol Download PDFInfo
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- CN106242954B CN106242954B CN201610620498.0A CN201610620498A CN106242954B CN 106242954 B CN106242954 B CN 106242954B CN 201610620498 A CN201610620498 A CN 201610620498A CN 106242954 B CN106242954 B CN 106242954B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/02—Preparation of ethers from oxiranes
- C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
Abstract
The invention belongs to polyether polyol synthesis technical fields, and in particular to a kind of preparation method of polyetheramine low molecular polyether polyalcohol.Only with 2- methyl-1,3-propanediol is initiator, be added base metal catalysts, first low temperature and epoxide reaction, then high temperature propylene oxide block to get.The present invention is in the polymerization, use 2- methyl-1,3-propanediol is as initiator, because of the regularity and symmetry of its structure, both ends activity is the same, when with epoxide polymerization, polyether structure is more regular, in amine sealing end, both ends activity is consistent, has the characteristics that amorphism, strong weatherability, stretch-proof, bending resistance are strong.This structure can make polyetheramine have low melting point, low viscosity, the good feature with auxiliary agent intersolubility.
Description
Technical field
The invention belongs to polyether polyol synthesis technical fields, and in particular to a kind of polyetheramine low molecular polyether is polynary
The preparation method of alcohol.
Background technique
Polyetheramine is that a kind of main chain is polyether polyol structure, and end active functional group is the polymer of amido.Polyetheramine
It is that ammonification obtains at high temperature under high pressure by the polyether polyol of polyethylene glycol, polypropylene glycol or ethylene glycol/propylene glycol copolymers
It arrives.Polyetheramine can be used as the high-performance curing agent of epoxy resin, for producing the composite material of high-intensitive, high tenacity；Tool
There is lower viscosity, when being applied to epoxide terrace or anticorrosive paint, it is possible to reduce solvent usage reduces system viscosity；As
The key component of polyurea materials has in the water-proof system of the concrete structures such as high-speed rail bridge, bridge spanning the sea, dam, large stadium
Many application examples, and show excellent performance etc..
All it is at present the low molecular polyether polyalcohol synthesized using traditional handicraft about the patent of polyetheramine, passes through difference
Technique improve amine conversion ratio or improve amine value.And traditional handicraft synthesis low molecular weight polycaprolactone ethoxylated polyhydric alcohol, from GPC spectrogram (see
As can be seen that molecular weight distribution is wide on Fig. 1), and there is the case where multiple miscellaneous peaks, prepares polyethers with such polyether polyol
Amine, amine ending ratio is low, active deviation is big, unstable product quality.
Polyetheramine is amine sealing end, and the reaction of polyetheramine is adjusted in polyether polyol molecular weight and structure different on main chain
A series of performances such as activity, toughness, viscosity and hydrophily, amido can be supplied to the possibility that polyetheramine is reacted with multiple compounds
Property.Its special molecular structure imparts the excellent comprehensive performance of polyetheramine.That is the structure and quality of polyether polyol
Directly determine the application field and mechanical property of a series of performances such as reactivity, toughness, viscosity and the hydrophily of polyetheramine
Index.
Summary of the invention
The object of the present invention is to provide a kind of polyetheramine preparation method of low molecular polyether polyalcohol, the polyethers of preparation
Polyalcohol low-unsaturation-degree, relatively narrow molecular weight distribution, while can also make polyetheramine that there is more preferably service performance.
Polyetheramine of the present invention is only the 3- the third two with 2- methyl-1 with the preparation method of low molecular polyether polyalcohol
Alcohol is initiator, be added base metal catalysts, first low temperature and epoxide reaction, then high temperature propylene oxide block to get.
The base metal catalysts are one or both of potassium hydroxide or sodium hydroxide, and dosage is 2- methyl-1,
The 0.3-0.5% of 3-propanediol, epoxides and propylene oxide three's gross mass.
The cryogenic temperature is 80-95 DEG C, and high-temperature temperature is 100-120 DEG C.
The epoxides is one or both of propylene oxide or ethylene oxide, and dosage is epoxides and epoxy
The 30-70% of propane gross mass.
The mass ratio of the 2- methyl-1,3-propanediol and epoxides is 90:50-610.
The polyetheramine of the present invention preparation method of low molecular polyether polyalcohol, steps are as follows:
(1) low temperature polymerization is reacted: 2- methyl-1,3-propanediol and base metal catalysts are added in a kettle first, stir
After mixing uniformly, nitrogen displacement 3-5 times is evacuated to vacuum pressure≤- 0.09MPa, stops vacuumizing, heating, when temperature reaches 80 DEG C,
Then it is continuously added to epoxides, carries out polymerization reaction, reaction temperature is controlled at 80-95 DEG C, and reaction pressure≤0.4MPa adds
After epoxides, the reaction was continued, waits after not changing 30 minutes to pressure stabilization, obtains intermediate polyether polyol；
(2) high temperature polymerization is reacted: the intermediate polyether polyol obtained after low temperature polymerization being heated, when temperature reaches 100
DEG C, be then continuously added to propylene oxide, carry out polymerization reaction sealing end, reaction temperature control at 100-120 DEG C, reaction pressure≤
0.4MPa, after propylene oxide adds, the reaction was continued, waits after not changing 30 minutes to pressure stabilization, and evacuated pressure≤-
Under 0.09MPa, unreacted propylene oxide monomer is sloughed, polymerization reaction is completed；Then 90 DEG C are cooled to, the production finished to polymerization
Phosphate aqueous solution is added in 80-90 DEG C of progress neutralization reaction in object, and adsorbent is added later and deviates from potassium/sodium ion, and in vacuum pressure
It is dehydrated under power≤- 0.09MPa, it is filtered, obtain required polyether polyol.
In the reaction of low temperature polymerization described in step (1), by controlling the quality of epoxides, gained intermediate polyethers is more
First alcohol molecular weight control is in 140-700.
Phosphate aqueous solution described in step (2) is the mixture of the phosphoric acid that concentration is 85% and distilled water, 85% phosphorus
Sour dosage is 2.3-2.6 times of base metal catalysts quality, and the dosage of distilled water is 2- methyl-1,3-propanediol, epoxides
With the 4-7% of propylene oxide three's gross mass.
Adsorbent described in step (2) is one of magnesium silicate, alumina silicate or aluminium-magnesium silicate or a variety of, and adsorbent is used
Amount is the 0.31-0.45% of 2- methyl-1,3-propanediol, epoxides and propylene oxide three's gross mass.
In the reaction of high temperature polymerization described in step (2), by controlling propylene oxide dosage, gained polyether polyol molecule
Amount control is in 200-1000.
By the amount of control phosphate aqueous solution, gained polyether polyol PH, which is controlled, to exist for neutralization reaction described in step (2)
5.5-6.9；Vacuum dehydration makes the control of polyether polyol moisture≤0.05%.
Compared with prior art, the present invention having the following beneficial effects:
(1) in the polymerization, using 2- methyl-1,3-propanediol is as initiator, because of the rule of its structure by the present invention
Whole property and symmetry, both ends activity is the same, and when with epoxide polymerization, polyether structure is more regular, and in amine sealing end, both ends are living
Property is consistent, has the characteristics that amorphism, strong weatherability, stretch-proof, bending resistance are strong.It is low that this structure can be such that polyetheramine has
Fusing point, low viscosity, the good feature with auxiliary agent intersolubility.
(2) two-stage process: low temperature polymerization was reacted before this, then back segment high temperature polymerization reaction, can from GPC spectrogram (see Fig. 2)
It to find out that such technique can make polyether polyol narrow molecular weight distribution, and is single-peak structure, more regular, quality is more stable.
(3) epoxide polymerization is used in front end, makes polyether polyol that there is different structures, different performances is provided.
Propylene oxide sealing end is added in rear end, keeps polyether polyol two-end structure consistent, the activity at both ends is also consistent, poly- in synthesis in this way
When ether amines, both ends amination simultaneously improves amine conversion ratio, improves amine value.
Detailed description of the invention
Fig. 1 is the GPC spectrogram of the low molecular polyether polyalcohol of traditional handicraft synthesis.
Fig. 2 is the GPC spectrogram for the low molecular polyether polyalcohol that the present invention synthesizes.
Specific embodiment
The present invention is described further with reference to embodiments.
Embodiment 1
2- methyl-1 is added in 2.5L autoclave at room temperature, 3-propanediol 270g, sodium hydroxide 2.4g are vacuumized
To -0.09MPa and nitrogen is replaced 3 times, is started stirring and is increased temperature to 80 DEG C, in the case where vacuum degree is -0.09MPa, continuously drips
Add 150g epoxides, oxypropylene 30g, ethylene oxide 120g.Reacting kettle inner pressure≤0.4MPa, reaction temperature are
At 80-95 DEG C, continues slaking reaction 1 hour after charging, obtain intermediate polyether polyol.Heating is heated to 100 DEG C, so
180g propylene oxide is continuously added dropwise afterwards, the reaction was continued a period of time, reaction temperature control at 100-120 DEG C, reaction pressure≤
0.4MPa waits after not changing 30 minutes to pressure stabilization, under evacuated pressure≤- 0.09MPa, sloughs unreacted propylene oxide
Monomer, polymerization reaction are completed.Be cooled to 90 DEG C hereinafter, be added 5.52g phosphoric acid and 30g distilled water composition phosphate aqueous solution,
At 90 DEG C, it is stirred to react 1 hour, 1.8g aluminum magnesium silicate is then added, stir 40 minutes, at vacuum pressure≤- 0.09MPa,
Vacuum dehydration 4h obtains polyether polyol a after filtering.Specific test data is shown in Table 1.
Embodiment 2
2- methyl-1 is added in 2.5L autoclave at room temperature, 3-propanediol 360g, potassium hydroxide 8.32g take out true
Empty to -0.09MPa, simultaneously nitrogen is replaced 3 times, is started stirring and is increased temperature to 80 DEG C, in the case where vacuum degree is -0.09MPa, continuously
860g epoxides, oxypropylene 420g, ethylene oxide 420g is added dropwise.Reacting kettle inner pressure≤0.4MPa, reaction temperature
It is to continue slaking reaction 1 hour after charging at 80-95 DEG C, obtain intermediate polyether polyol.Heating is heated to 100 DEG C,
Then 860g propylene oxide is continuously added dropwise, the reaction was continued a period of time, reaction temperature control at 100-120 DEG C, reaction pressure≤
0.4MPa waits after not changing 30 minutes to pressure stabilization, under evacuated pressure≤- 0.09MPa, sloughs unreacted propylene oxide
Monomer, polymerization reaction are completed.Be cooled to 90 DEG C hereinafter, be added 19.9g phosphoric acid and 104g distilled water composition phosphate aqueous solution,
At 90 DEG C, it is stirred to react 1 hour, 7.28g magnesium silicate is then added, stir 40 minutes, at vacuum pressure≤- 0.09MPa, very
Sky dehydration 3h, obtains polyether polyol b after filtering.Specific test data is shown in Table 1.
Embodiment 3
2- methyl-1 is added in 2.5L autoclave at room temperature, 3-propanediol 180g, potassium hydroxide 8g are vacuumized
To -0.09MPa and nitrogen is replaced 3 times, is started stirring and is increased temperature to 80 DEG C, in the case where vacuum degree is -0.09MPa, continuously drips
Add 1229g epoxides, is all propylene oxide.Reacting kettle inner pressure≤0.4MPa, reaction temperature are to have fed at 80-95 DEG C
Continue slaking reaction 1 hour after finishing, obtains intermediate polyether polyol.Heating is heated to 100 DEG C, and 600g ring is then continuously added dropwise
Ethylene Oxide, the reaction was continued a period of time, and reaction temperature is controlled at 100-120 DEG C, and reaction pressure≤0.4MPa waits to pressure and stablizes
After not changing 30 minutes, under evacuated pressure≤- 0.09MPa, unreacted propylene oxide monomer is sloughed, polymerization reaction is completed.
90 DEG C are cooled to hereinafter, it is small to be stirred to react 1 at 90 DEG C for the phosphate aqueous solution that 19.2g phosphoric acid and 100g distilled water composition is added
When, 8g alumina silicate is then added, stirs 40 minutes, at vacuum pressure≤- 0.09MPa, vacuum dehydration 3h is gathered after filtering
Ethoxylated polyhydric alcohol c.Specific test data is shown in Table 1.
1 embodiment 1-3 of table prepares polyether polyol test index
Claims (8)
1. a kind of polyetheramine preparation method of low molecular polyether polyalcohol, it is characterised in that only with 2- methyl-1,3- the third two
Alcohol is initiator, be added base metal catalysts, first low temperature and epoxide reaction, then high temperature propylene oxide block to get；
The cryogenic temperature is 80-95 DEG C, and high-temperature temperature is 100-120 DEG C；
The epoxides is one or both of propylene oxide or ethylene oxide, and dosage is epoxides and propylene oxide
The 30-70% of gross mass.
2. the polyetheramine according to claim 1 preparation method of low molecular polyether polyalcohol, it is characterised in that described
Base metal catalysts be one or both of potassium hydroxide or sodium hydroxide, dosage be 2- methyl-1,3-propanediol, epoxy
The 0.3-0.5% of compound and propylene oxide three's gross mass.
3. the polyetheramine according to claim 1 preparation method of low molecular polyether polyalcohol, it is characterised in that described
2- methyl-1,3-propanediol and epoxides mass ratio be 90:50-610.
4. the polyetheramine according to claim 1 to 3 preparation method of low molecular polyether polyalcohol, feature exist
In steps are as follows:
(1) low temperature polymerization is reacted: 2- methyl-1,3-propanediol and base metal catalysts is added in a kettle first, stirring is equal
After even, nitrogen displacement 3-5 times is evacuated to vacuum pressure≤- 0.09MPa, stops vacuumizing, heating, when temperature reaches 80 DEG C, then
It is continuously added to epoxides, carries out polymerization reaction, reaction temperature is controlled at 80-95 DEG C, and reaction pressure≤0.4MPa adds epoxy
After compound, the reaction was continued, waits after not changing 30 minutes to pressure stabilization, obtains intermediate polyether polyol；
(2) high temperature polymerization is reacted: the intermediate polyether polyol obtained after low temperature polymerization being heated, when temperature reaches 100 DEG C, so
After be continuously added to propylene oxide, carry out polymerization reaction sealing end, reaction temperature is controlled at 100-120 DEG C, reaction pressure≤0.4MPa,
After propylene oxide adds, the reaction was continued, waits after not changing 30 minutes to pressure stabilization, under evacuated pressure≤- 0.09MPa, takes off
Unreacted propylene oxide monomer is gone, polymerization reaction is completed；Then 90 DEG C are cooled to, phosphoric acid water is added to the product that polymerization finishes
Adsorbent is added later and deviates from potassium/sodium ion in 80-90 DEG C of progress neutralization reaction for solution, and in vacuum pressure≤- 0.09MPa
Lower dehydration, is filtered it, obtains required polyether polyol.
5. the polyetheramine according to claim 4 preparation method of low molecular polyether polyalcohol, it is characterised in that step
(1) the intermediate polyether polyol molecular weight described in is controlled in 140-700.
6. the polyetheramine according to claim 4 preparation method of low molecular polyether polyalcohol, it is characterised in that step
(2) phosphate aqueous solution described in is the mixture of the phosphoric acid that concentration is 85% and distilled water, and 85% phosphoric acid dosage is alkali metal
2.3-2.6 times of catalyst quality, the dosage of distilled water are 2- methyl-1,3-propanediol, epoxides and propylene oxide three
The 4-7% of gross mass.
7. the polyetheramine according to claim 4 preparation method of low molecular polyether polyalcohol, it is characterised in that step
(2) adsorbent described in is one of magnesium silicate, alumina silicate or aluminium-magnesium silicate or a variety of, and adsorbent amount is 2- methyl-
The 0.31-0.45% of 1,3- propylene glycol, epoxides and propylene oxide three's gross mass.
8. the polyetheramine according to claim 4 preparation method of low molecular polyether polyalcohol, it is characterised in that step
(2) the polyether polyol molecular weight described in is controlled in 200-1000.
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| CN110437725A (en) * | 2019-08-14 | 2019-11-12 | 四川暄洋新材料科技有限公司 | It is a kind of to pass through silicate modified polyetheramine polyurethane antifouling paint and its application |
| CN111057228A (en) * | 2019-12-13 | 2020-04-24 | 张家港美景荣化学工业有限公司 | Preparation method of low molecular weight polyether polyol |
| CN114316252B (en) * | 2021-12-10 | 2023-05-02 | 湖北三江航天江河化工科技有限公司 | Telechelic type rapid thermal/photo-curing ablation-resistant resin and synthesis method thereof |
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