CN104974340B - The preparation method of the polyether polyol with high activity containing ester bond in main chain - Google Patents
The preparation method of the polyether polyol with high activity containing ester bond in main chain Download PDFInfo
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- CN104974340B CN104974340B CN201510358717.8A CN201510358717A CN104974340B CN 104974340 B CN104974340 B CN 104974340B CN 201510358717 A CN201510358717 A CN 201510358717A CN 104974340 B CN104974340 B CN 104974340B
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Abstract
The invention belongs to polyhydric alcohol technical field, and in particular to the preparation method of the polyether polyol with high activity containing ester bond in a kind of main chain.Described preparation method is that Oleic acid and terminal hydroxy group material are carried out esterification in the presence of a catalyst, and the product that esterification is obtained carries out polyreaction in the presence of auxiliary agent with expoxy propane, the polyether polyol with high activity containing ester bond is obtained after process.Polyhydric alcohol prepared by the present invention contains more ehter bond, so as to ensure which as the activity of raw material, being capable of room temperature foaming.Due to containing ester bond in the main chain of product of the present invention, so as to there is good intermiscibility with foaming agent and auxiliary agent, can store for a long time, it is excellent as the pliability of foamed product obtained in raw material.Even if the pliability of foamed product is not interfered with yet as foaming agent using water.
Description
Technical field
The invention belongs to polyhydric alcohol technical field, and in particular to the polyether polyol with high activity containing ester bond in a kind of main chain
Preparation method.
Background technology
The species of polyhydric alcohol is more in the market, but, the spread in performance of polyhydric alcohol is uneven, and particularly combination property is good
Good polyhydric alcohol is even more few.Polyhydric alcohol performance of the prior art is more single, and the shelf characteric of some polyhydric alcohol is good, has
The pliability of a little polyhydric alcohol is preferable, and some polyhydric alcohol are preferable with the intermiscibility of foaming agent and auxiliary agent etc., and single performance causes
Using being very restricted.Need that a kind of activity of exploitation is high badly, shelf characteric is good, and have with foaming agent and auxiliary agent and well mix
The polyether polyol with high activity of property.
The content of the invention
It is an object of the invention to provide in a kind of main chain, contain the preparation method of the polyether polyol with high activity of ester bond, preparation
Polyhydric alcohol activity is high, and shelf characteric is good, and has good intermiscibility with foaming agent and auxiliary agent, steeps as obtained in raw material
The pliability of foam product is excellent.
In main chain of the present invention, the preparation method of the polyether polyol with high activity containing ester bond, is by Oleic acid and terminal hydroxy group
Material carries out esterification in the presence of a catalyst, and the product that esterification is obtained is gathered in the presence of auxiliary agent with expoxy propane
Reaction is closed, the polyether polyol with high activity containing ester bond after process, is obtained.
Described terminal hydroxy group material is one or more in ethylene glycol, Propylene Glycol or glycerol.
Described catalyst is sulphuric acid or p-methyl benzenesulfonic acid.
100～150 DEG C of described esterification reaction temperature, 0.3～0.4MPa of reaction pressure, 8～12h of response time.
Described auxiliary agent is potassium tert-butoxide or potassium hydroxide.
100～120 DEG C of described polymeric reaction temperature, 0.1～0.4MPa of reaction pressure, 4～8h of response time.
Described Oleic acid, terminal hydroxy group material, the mass ratio 100～105 of catalyst:20～70:1～5.
Product that described esterification is obtained, expoxy propane, the mass ratio 15～35 of auxiliary agent:200～500:1～4.
The chemical equation of the present invention is as follows：
(1) esterification：
(2) polyreaction：
Wherein, R represents H, CH3Or CH2OH；N represents the ehter bond number in the polyreaction degree of polymerization, namely a molecule, and n is not
Less than 30.
Ether bond content in polyhydric alcohol is the important indicator for weighing polyol quality, and ether bond content is more, polyhydric alcohol activity
It is higher.
Beneficial effects of the present invention are as follows：
Polyhydric alcohol prepared by the present invention contains more ehter bond, so as to ensure which as the activity of raw material, being capable of room temperature
Bubble.Due to containing ester bond in the main chain of product of the present invention, so as to there is good intermiscibility with foaming agent and auxiliary agent, can be long-term
Storage, it is excellent as the pliability of foamed product obtained in raw material.Even if foam is not interfered with yet as foaming agent using water
The pliability of product.
Specific embodiment
With reference to embodiments the present invention is described further.
Embodiment 1
(1) esterification：
565g Oleic acid, 150g ethylene glycol, 10g sulphuric acid are warming up to 130 DEG C of reaction 10h, and reaction pressure is 0.34MPa, reaction
After the completion of, wash or weak base washes resulting material, until surveying its pH>7, evacuation 0.1MPa, are warming up to 80 DEG C of dehydration 1h, continue to rise
120 DEG C of dehydration 2h of temperature, obtain oleic acid glycol ester.
(2) polyreaction：
Under nitrogen protection, addition 50g oleic acid glycol esters, 3g potassium tert-butoxides, 500g expoxy propane in 5L reactors,
100 DEG C are warming up to, 0.4MPa reaction 4h obtain thick polyethers.
(3) thick polyethers is neutralized, is refined：
Temperature in the kettle is down to 80 DEG C, adds pure water 20g, stirs 10min, adds 50wt.% phosphoric acid solutions 4g neutralizations, stirring
30min is until survey pH=5.0, addition 3g aluminium silicate stirs 30min, opens vacuum pump dehydration, after most of water is sloughed, rises
Temperature continues dehydration, bubbling to 120 DEG C.Shui Fen≤0.05% is surveyed in sampling, and dehydration terminates, and is filtrated to get polyethers finished product.
Obtained polyethers：
Hydroxyl value：22.8mgKOH/g, acid number：0.05mgKOH/g, moisture：0.03%, viscosity：1670mPas/25 DEG C, potassium from
Son：3ppm, colourity：30APHA.Ehter bond number n in one molecule polyether polyol is 56.
Embodiment 2
(1) esterification：
565g Oleic acid, 304g Propylene Glycol, 15g p-methyl benzenesulfonic acid are warming up to 100 DEG C of reaction 12h, and reaction pressure is
0.4MPa, after the completion of reaction, washing or weak base wash resulting material, until surveying its pH>7, evacuation 0.1MPa, are warming up to 80 DEG C and take off
Water 1h, continues the 130 DEG C of dehydration 2h that heat up, obtains Oleic acid propylene glycol ester.
(2) polyreaction：
Under nitrogen protection, addition 60g Oleic acid propylene glycol esters, 3g potassium hydroxide, 600g expoxy propane in 5L reactors,
110 DEG C are warming up to, 0.24MPa reaction 6h obtain thick polyethers.
(3) thick polyethers is neutralized, is refined：
Temperature in the kettle is down to 80 DEG C, adds pure water 20g, stirs 10min, adds 50wt.% phosphoric acid solutions 4g neutralizations, stirring
30min is until survey pH=5.0, addition 3g aluminium silicate stirs 30min, opens vacuum pump dehydration, after most of water is sloughed, rises
Temperature continues dehydration, bubbling to 120 DEG C.Shui Fen≤0.05% is surveyed in sampling, and dehydration terminates, and is filtrated to get polyethers finished product.
Obtained polyethers：
Hydroxyl value：23.1mgKOH/g, acid number：0.05mgKOH/g, moisture：0.03%, viscosity：1660mPas/25 DEG C, potassium from
Son：3ppm, colourity：40APHA.Ehter bond number n in one molecule polyether polyol is 58.
Embodiment 3
(1) esterification：
565g Oleic acid, 368g glycerol, 20g sulphuric acid are warming up to 150 DEG C of reaction 8h, and reaction pressure is 0.3MPa, has been reacted
Cheng Hou, washing or weak base wash resulting material, until surveying its pH>7, evacuation 0.1MPa, are warming up to 80 DEG C of dehydration 1h, continue to heat up
130 DEG C of dehydration 2h, obtain Oleic acid glycerine ester.
(2) polyreaction：
Under nitrogen protection, addition 40g Oleic acid glycerine esters, 6g potassium hydroxide, 900g expoxy propane in 5L reactors,
120 DEG C are warming up to, 0.4MPa reaction 5h obtain thick polyethers.
(3) thick polyethers is neutralized, is refined：
Temperature in the kettle is down to 80 DEG C, adds pure water 20g, stirs 10min, adds 50wt.% phosphoric acid solutions 4g neutralizations, stirring
30min is until survey pH=5.0, addition 3g aluminium silicate stirs 30min, opens vacuum pump dehydration, after most of water is sloughed, rises
Temperature continues dehydration, bubbling to 120 DEG C.Shui Fen≤0.05% is surveyed in sampling, and dehydration terminates, and is filtrated to get polyethers finished product.
Obtained polyethers：
Hydroxyl value：22.9mgKOH/g, acid number：0.05mgKOH/g, moisture：0.03%, viscosity：1670mPas/25 DEG C, potassium from
Son：3ppm, colourity：30APHA.Ehter bond number n in one molecule polyether polyol is 138.
Claims (5)
1. the preparation method of the polyether polyol with high activity of ester bond is contained in a kind of main chain, it is characterised in that：By Oleic acid and terminal hydroxy group
Material carries out esterification in the presence of a catalyst, and the product that esterification is obtained is gathered in the presence of auxiliary agent with expoxy propane
Reaction is closed, the polyether polyol with high activity containing ester bond after process, is obtained；
Terminal hydroxy group material is one or more in ethylene glycol, Propylene Glycol or glycerol；
100～150 DEG C of esterification reaction temperature, 0.3～0.4MPa of reaction pressure, 8～12h of response time；
100～120 DEG C of polymeric reaction temperature, 0.1～0.4MPa of reaction pressure, 4～8h of response time.
2. the preparation method of the polyether polyol with high activity of ester bond is contained in main chain according to claim 1, it is characterised in that：
Catalyst is sulphuric acid or p-methyl benzenesulfonic acid.
3. the preparation method of the polyether polyol with high activity of ester bond is contained in main chain according to claim 1, it is characterised in that：
Auxiliary agent is potassium tert-butoxide or potassium hydroxide.
4. the preparation method of the polyether polyol with high activity of ester bond is contained in main chain according to claim 1, it is characterised in that：
Oleic acid, terminal hydroxy group material, the mass ratio 100～105 of catalyst:20～70:1～5.
5. the preparation method of the polyether polyol with high activity of ester bond is contained in main chain according to claim 1, it is characterised in that：
Product that esterification is obtained, expoxy propane, the mass ratio 15～35 of auxiliary agent:200～500:1～4.
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| CN107162905A (en) * | 2017-06-08 | 2017-09-15 | 西安万德能源化学股份有限公司 | Ester type diesel antiwear additive and preparation method thereof |
| CN108822289A (en) * | 2018-07-12 | 2018-11-16 | 广州汇科精细化工有限公司 | Composite catalyst and its application and the method for preparing water-soluble aliphatic ester |
| CN110951067A (en) * | 2019-12-11 | 2020-04-03 | 浙江皇马新材料科技有限公司 | Method for preparing polyether polyol by using high-acid-value waste oil |
| CN112457480B (en) * | 2020-11-26 | 2023-09-26 | 山东尚正新材料科技股份有限公司 | Preparation method of bio-based modified high-activity polyether polyol |
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| CN101747192A (en) * | 2009-12-15 | 2010-06-23 | 浙江合诚化学有限公司 | Method for synthesizing polyethylene glycol (PEG) oleate |
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| CN102875793A (en) * | 2012-09-24 | 2013-01-16 | 辽宁科技大学 | Synthesis and application of sorbitan monooleate polyoxyethylene ether for iron ore flotation |
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| CN101747192A (en) * | 2009-12-15 | 2010-06-23 | 浙江合诚化学有限公司 | Method for synthesizing polyethylene glycol (PEG) oleate |
| CN102127217A (en) * | 2010-12-16 | 2011-07-20 | 南京威尔化工有限公司 | Method for synthesizing polysorbate 80(I) for injection |
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