CN107216453A - A kind of bisphenol A polyether and preparation method thereof - Google Patents
A kind of bisphenol A polyether and preparation method thereof Download PDFInfo
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- CN107216453A CN107216453A CN201710464027.XA CN201710464027A CN107216453A CN 107216453 A CN107216453 A CN 107216453A CN 201710464027 A CN201710464027 A CN 201710464027A CN 107216453 A CN107216453 A CN 107216453A
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- Prior art keywords
- bisphenol
- antioxidant
- polyether
- preparation
- epoxyalkane
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2612—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aromatic or arylaliphatic hydroxyl groups
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2696—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the process or apparatus used
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
Abstract
The invention provides a kind of bisphenol A polyether and preparation method thereof, the preparation method technique of bisphenol A polyether of the present invention is simple, reacted using bisphenol-A and epoxyalkane, through overcuring, degassing, add antioxidant and obtain bisphenol A polyether product, the inventive method can obtain that hydroxyl value is low using special process, and viscosity is low, the low uniform bisphenol A polyether product of colourity.Bisphenol A polyether product of the present invention, hydroxyl value is low, and viscosity is low, and colourity is low, can keep uniform and stable for a long time, can preferably carry out subsequent applications, is more conducive to mix with unclassified stores.
Description
Technical field
The present invention relates to functional polymer technical field, in particular to a kind of bisphenol A polyether and its preparation side
Method.
Background technology
Bisphenol A polyether polyalcohol has important application in synthetic resin field, can be used as the monomer of synthetic resin, may be used also
It is used as the dressing agent of high molecular polymerization chain.Due to containing aromatic ring in molecule, therefore it can make that the resin structure of synthesis is more stable, property
Can be more excellent, it can be made into anti-seismic material, light-sensitive material, bonding material etc..The main application division of bisphenol A polyether polyalcohol is such as
Under：
1st, with the various resins of binary acid condensation synthesis：
The performance for being esterified the resin formed by dihydric alcohol, binary acid directly depends on alcohol, the molecular structure of acid, and dihydric alcohol
Molecular structure be particularly important.It is industrial with more dihydric alcohol is ethylene glycol, but glycol molecule is simple in construction, conjunction
Into resin its structure it is also more single.And BA PPGs improve synthesis tree due to containing aromatic ring in its molecule, well
The structure and performance of fat.
Hirakouchi et al. has found that the elasticity that bisphenol A polyether polyalcohol is synthesized after being condensed with aromatic binary carboxylic acid is set
Fat is widely used in the fields such as machinery, building, automobile making, can completely cut off noise, reduces harmful vibration.
2nd, the carboxylate with unsaturated acids is used as synthetic resin monomer：
The unsaturated acid esterification such as bisphenol A polyether polyalcohol and acrylic acid, methacrylic acid, can be made into several functions high score
Sub- polymerized monomer.Wherein, the polymer of the double methyl methacrylate of BA PPGs is because with good refractive index, printing opacity
Property, moderate solidification temperature and hardening time, thus can as optical fiber clad material；It can be made into light-sensitive material, use
In manufacture optical element；It still prepares the principal monomer of anaerobic adhesive, and the anaerobic adhesive of synthesis is in the case where completely cutting off air, in room
Wen Shineng rapid curings, solvent-free, nontoxic, heat-resisting, acid and alkali-resistance and tablet corrosion vibration resistance, impact, are widely used as machinery, vapour
Car, electric, aircraft etc. are with the adhesive in process；It may also be fabricated which curable liquid resin composition, as primer base,
The strip base material of secondary coating, optical fiber；Further, since its biocompatibility preferably, also acts as traditional tooth
Enamel adhesive is repaired by section.
3rd, as the dressing agent and additive of high molecular polymer chain：
Bisphenol A polyether polyalcohol is bonded in high molecular polymer chain by a certain percentage, can have polymer more preferable
Intensity, elasticity, bonding force and processability.For example, BA PPGs are with different mol ratio and terephthalic acid polymerization, bisphenol-A
Group is inserted into polyester chain, it is possible to decrease the crystalline rate of polybutyleneterephthalate, polymer is had good mechanicalness
Can, electric property and physical and chemical performance, the engineering plastics being made are widely used in automobile making, electric and electronic field.
But the bisphenol A polyether product viscosity in correlation technique is excessive, it is unsuitable for when subsequently using and unclassified stores
Mixing, and preparation technology is complicated, and reaction side reaction is more, causes gained bisphenol A polyether product hydroxyl value greatly, colourity is high, after influence
Continuous using effect.In addition, the easy aging denaturation of bisphenol A polyether product in correlation technique, the term of validity is short, it is impossible to retentivity steady in a long-term
Energy.
In view of this, it is special to propose the present invention.
The content of the invention
The first object of the present invention is to provide a kind of preparation method of bisphenol A polyether, and this method technique is simple, can obtain
Low to hydroxyl value, viscosity is low, the low uniform bisphenol A polyether product of colourity.
The second object of the present invention is to provide pair that a kind of preparation method using above-mentioned bisphenol A polyether is prepared
Phenol A polyether products, described bisphenol A polyether product, hydroxyl value is low, and viscosity is low, and colourity is low, can keep uniform and stable for a long time,
Subsequent applications can be preferably carried out, are more conducive to mix with unclassified stores.
In order to realize the above-mentioned purpose of the present invention, spy uses following technical scheme：
A kind of preparation method of bisphenol A polyether, under vacuo, alkali is added into bisphenol-A, is sufficiently stirred for, and adds alkylene oxide
Hydrocarbon, is cured, and degassing adds antioxidant, obtains a kind of bisphenol A polyether product.
The preparation method technique of bisphenol A polyether of the present invention is simple, is reacted using bisphenol-A and epoxyalkane, through overcuring, takes off
Gas, adds antioxidant and obtains bisphenol A polyether product, and the inventive method can obtain that hydroxyl value is low using special process, and viscosity is low, color
The low uniform bisphenol A polyether product of degree.
Alternatively, the mass ratio of the bisphenol-A and epoxyalkane is 30-50：40-60, preferably 35-45：45-55, enters
One step is preferably 42：50.
Alternatively, the vacuum of the vacuum reaches more than -0.098MPa, preferably reaches more than -0.099MPa.
Alternatively, the alkali includes the one or more in organic base and inorganic base, preferably includes one in inorganic strong alkali
Plant or a variety of, more preferably KOH.
Alternatively, the consumption of the alkali is less than the 1% of the quality that always feeds intake of bisphenol-A and epoxyalkane, is preferably
0.5%.
Alternatively, the time of the stirring is more than 30min, preferably 40min.
Alternatively, the epoxyalkane includes the one or more in C2-C6 epoxyalkane, preferably includes C2-C4 epoxies
One or more in alkane, more preferably oxirane.
Alternatively, the system pressure for adding epoxyalkane is controlled in below 0.2MPa.
Alternatively, PART EPOXY alkane is first added, heats up afterwards, adds residual epoxide alkane.
Preferably, the PART EPOXY alkane be the total consumption of epoxyalkane less than 30%, preferably 10%-20% with
Under, more preferably 10%.
Preferably, the temperature of the heating is more than 120 DEG C, more preferably preferably 120-150 DEG C, 130-140
℃。
Alternatively, the system temperature of the curing is controlled more than 120 DEG C, is preferably controlled in 120-150 DEG C, further excellent
Selected control system is at 130-140 DEG C.
Alternatively, the curing time is more than 1h, preferably 1h.
Alternatively, control system pressure is below 0.5MPa during the curing.
Alternatively, the temperature control of the degassing is preferably controlled in 120-150 DEG C more than 120 DEG C, further preferably control
System is at 130-140 DEG C.
Alternatively, the time of the degassing is more than 1h, preferably 1h.
Alternatively, the antioxidant includes one in aromatic amine antioxidant, Hinered phenols antioxidant and auxiliary antioxidant
Plant or a variety of, preferably include no BHT antioxidant, compound antioxidant and without the one or more in amine environment-friendly type compound antioxidant；
Alternatively, the consumption of the antioxidant is less than the 0.5% of the quality that always feeds intake of bisphenol-A and epoxyalkane, preferably
For 0.2%.
Alternatively, antioxidant is added after system is cooled.
Preferably, system temperature is cooled to 70-80 DEG C, adds antioxidant.
Alternatively, add and system vacuum inspection is carried out after alkali.
Alternatively, add after antioxidant, stirring is fully melted to antioxidant, obtains a kind of bisphenol A polyether product.
The bisphenol A polyether product prepared using a kind of preparation method of above-mentioned bisphenol A polyether.
Bisphenol A polyether product of the present invention, hydroxyl value is low, and viscosity is low, and colourity is low, uniform and stable, can preferably carry out follow-up
Using, be more conducive to mixed with unclassified stores.
Compared with prior art, beneficial effects of the present invention are：
The preparation method technique of bisphenol A polyether of the present invention is simple, is reacted using bisphenol-A and epoxyalkane, through overcuring, takes off
Gas, adds antioxidant and obtains bisphenol A polyether product, and the inventive method can obtain that hydroxyl value is low using special process, and viscosity is low, color
The low uniform bisphenol A polyether product of degree.Bisphenol A polyether product of the present invention, hydroxyl value is low, and viscosity is low, and colourity is low, uniform and stable, energy
It is enough preferably to carry out subsequent applications, it is more conducive to mix with unclassified stores.
Embodiment
Technical scheme is clearly and completely described below in conjunction with embodiment, but ability
Field technique personnel will be understood that following described embodiment is a part of embodiment of the invention, rather than whole embodiments,
The present invention is merely to illustrate, and is not construed as limiting the scope of the present invention.Based on the embodiment in the present invention, the common skill in this area
The every other embodiment that art personnel are obtained under the premise of creative work is not made, belongs to the model that the present invention is protected
Enclose.Unreceipted actual conditions person in embodiment, the condition advised according to normal condition or manufacturer is carried out.Agents useful for same or instrument
Unreceipted production firm person, is the conventional products that can be obtained by commercially available purchase.
The specific embodiment of the invention provides a kind of preparation method of bisphenol A polyether, under vacuo, adds into bisphenol-A
Enter alkali, be sufficiently stirred for, add epoxyalkane, cure, degassing adds antioxidant, obtains a kind of bisphenol A polyether product.
The preparation method technique of bisphenol A polyether of the present invention is simple, is reacted using bisphenol-A and epoxyalkane, through overcuring, takes off
Gas, adds antioxidant and obtains bisphenol A polyether product, and the inventive method can obtain that hydroxyl value is low using special process, and viscosity is low, color
The low uniform bisphenol A polyether product of degree.
In a kind of preferred embodiment of the present invention, the mass ratio of the bisphenol-A and epoxyalkane is 30-50：40-
60, preferably 35-45：45-55, more preferably 42：50.
Using the epoxyalkane of specific consumption, its reaction efficiency with bisphenol-A is favorably improved, accessory substance is reduced, obtains
The bisphenol A polyether product of low hydroxyl value, low viscosity and low colourity.
In a kind of preferred embodiment of the present invention, the vacuum of the vacuum reaches more than -0.098MPa, preferably
Reach more than -0.099MPa.
In a kind of preferred embodiment of the present invention, the alkali includes one kind or many in organic base and inorganic base
Kind, preferably include the one or more in inorganic strong alkali, more preferably KOH.
Using alkali as catalyst, help lend some impetus to bisphenol-A and epoxyalkane fully reacts, improve reaction efficiency, reduce
Accessory substance, obtains the bisphenol A polyether product of low hydroxyl value, low viscosity and low colourity.
In a kind of preferred embodiment of the present invention, the consumption of the alkali always feeds intake for bisphenol-A and epoxyalkane
Less than the 1% of quality, preferably 0.5%.
Using the alkali of specific consumption, help lend some impetus to bisphenol-A and epoxyalkane fully reacts, improve reaction efficiency, reduce
Accessory substance, obtains the bisphenol A polyether product of low hydroxyl value, low viscosity and low colourity.
In a kind of preferred embodiment of the present invention, the time of the stirring is more than 30min, preferably 40min.
Using specific mixing time, help to make bisphenol-A and alkali be sufficiently mixed uniformly, further improve reaction efficiency, subtract
Few accessory substance, obtains the bisphenol A polyether product of low hydroxyl value, low viscosity and low colourity.
In a kind of preferred embodiment of the present invention, the epoxyalkane includes one kind in C2-C6 epoxyalkane
Or it is a variety of, preferably include the one or more in C2-C4 epoxyalkane, more preferably oxirane.
Using specific epoxyalkane, be favorably improved its reaction efficiency with bisphenol-A, reduce accessory substance, obtain low hydroxyl value,
The bisphenol A polyether product of low viscosity and low colourity.
In a kind of preferred embodiment of the present invention, the system pressure for adding epoxyalkane is controlled in 0.2MPa
Below.
In a kind of preferred embodiment of the present invention, PART EPOXY alkane is first added, heats up afterwards, adds residue
Epoxyalkane.
Preferably, the PART EPOXY alkane be the total consumption of epoxyalkane less than 30%, preferably 10%-20% with
Under, more preferably 10%.
Preferably, the temperature of the heating is more than 120 DEG C, more preferably preferably 120-150 DEG C, 130-140
℃。
Using specific epoxyalkane feeding process, help lend some impetus to bisphenol-A and epoxyalkane fully reacts, improve reaction effect
Rate, reduces accessory substance, obtains the bisphenol A polyether product of low hydroxyl value, low viscosity and low colourity.
In a kind of preferred embodiment of the present invention, the system temperature of the curing is controlled more than 120 DEG C, preferably
Control is at 120-150 DEG C, and further preferably control is at 130-140 DEG C.
Curing temperature is reduced, helps to obtain the lower bisphenol A polyether product of viscosity, but also leads to reaction simultaneously and is not filled
Point, unreacting material and accessory substance increase, the performance of influence gained bisphenol A polyether product.
In a kind of preferred embodiment of the present invention, the curing time is more than 1h, preferably 1h.
In a kind of preferred embodiment of the present invention, control system pressure is below 0.5MPa during the curing.
Using specific curing temperature, curing time and pressure, cured, helped lend some impetus to double after epoxyalkane addition
Phenol A and epoxyalkane fully react, and improve reaction efficiency, reduce accessory substance, obtain the bis-phenol of low hydroxyl value, low viscosity and low colourity
A polyether products.
In a kind of preferred embodiment of the present invention, the temperature control of the degassing is preferably controlled more than 120 DEG C
At 120-150 DEG C, further preferably control is at 130-140 DEG C.
In a kind of preferred embodiment of the present invention, the time of the degassing is more than 1h, preferably 1h.
Using specific degassing temperature and time, help to remove unreacting material and accessory substance, it is possible to increase gained bisphenol-A
Polyethers purity.
In a kind of preferred embodiment of the present invention, the antioxidant includes aromatic amine antioxidant, Hinered phenols
One or more in antioxidant and auxiliary antioxidant, preferably include the third generation without BHT antioxidant, compound antioxidant and forth generation
Without the one or more in amine environment-friendly type compound antioxidant, such as the compound antioxidant used in the specific embodiment of the invention by
Antioxidant 5057 and the compounding of antioxidant 1135 are prepared, and manufacturer is Panjin Yun Jia Chemical Co., Ltd.s.
, can be fully miscible with gained bisphenol A polyether product using specific antioxidant, bisphenol A polyether can be effectively improved
The temperature resistant capability of product, improves initial oxidation temperature, while can effectively prevent color and luster variation issue.
In a kind of preferred embodiment of the present invention, the consumption of the antioxidant is total for bisphenol-A and epoxyalkane
Less than the 0.5% of the quality that feeds intake, preferably 0.2%.
Using specific antioxidant consumption, the property of gained bisphenol A polyether is not interfered with, bisphenol A polyether can be effectively improved
The temperature resistant capability of product, improves initial oxidation temperature, while can effectively prevent color and luster variation issue.
In a kind of preferred embodiment of the present invention, antioxidant is added after system is cooled.
Preferably, system temperature is cooled to 70-80 DEG C, adds antioxidant.
Antioxidant is added after cooling, helps to reduce antioxidant denaturation loss, while ensureing antioxidant fully and bisphenol-A
Polyethers dissolves each other.
In a kind of preferred embodiment of the present invention, add and system vacuum inspection is carried out after alkali.
The system vacuum inspection includes reaction vessel, outer circulation pump and all valves of system, pipeline No leakage, vavuum pump
Normal operation, vacuum reaches sets requirement.
In a kind of preferred embodiment of the present invention, add after antioxidant, stirring is fully melted to antioxidant, is obtained
A kind of bisphenol A polyether product.
The bisphenol A polyether product prepared using a kind of preparation method of above-mentioned bisphenol A polyether.
Bisphenol A polyether product of the present invention, hydroxyl value is low, and viscosity is low, and colourity is low, uniform and stable, can preferably carry out follow-up
Using, be more conducive to mixed with unclassified stores.
Embodiment 1
A kind of preparation method of bisphenol A polyether, including：
First, each raw material dosage is as shown in table 1：
Each raw material dosage of bisphenol A polyether preparation method of 1 embodiment of the present invention of table 1
2nd, technological process：
1st, check：
Kettle is clean, reactor, outer circulation pump and all valves of system, pipeline No leakage, vavuum pump normal operation, vacuum
Reach more than -0.098MPa, such as -0.099MPa, it is more low better.Supreme series-produced pure material in reactor, pipeline.
2nd, feed intake：
Put into BPA.
3rd, KOH is added：
KOH is added by inventory, can be pumped into and also directly pour into, first-class blind plate after KOH is added, negative pressure displacement 2 times is such as anti-
The good then negative pressure of kettle sealing is answered to feed.Plus start charging after KOH stirrings 30min.
Note：Slowly vacuum valve is driven during displacement, while observing visor, easily strip, shutoff valve is wanted after reactor outer circulation pipeline displacement
It is malleation in door, holding tube line.
4th, EO is entered：
Control system pressure is below 0.2MPa, first adds the 30% of the total consumptions of EO, system temperature is warming up into 120 DEG C,
System temperature is kept, remaining EO is added.
5th, cure, deaerate：
It is 120 DEG C to keep system temperature, cures 1h, and it is below 0.05MPa that kettle pressure is kept during curing, then controls the temperature to be
120 DEG C, it is below 0.05MPa, vacuum outgas 1h to keep kettle pressure.
6th, cooling plus antioxidant：
70-80 DEG C is cooled to, BHT is added, stirring is melted completely to BHT, and blowing obtains a kind of bisphenol A polyether product.
The index of bisphenol A polyether product is as follows obtained by the present embodiment：
Outward appearance is transparent slightly yellow liquid, and colourity is 24APHA, and pH is 6.8, and hydroxyl value is viscosity at 164mgKOH/g, 25 DEG C
For 1550CPS, water content is 0.031%.
Embodiment 2
A kind of preparation method of bisphenol A polyether, including：
First, each raw material dosage is as shown in table 2：
Each raw material dosage of bisphenol A polyether preparation method of 2 embodiment of the present invention of table 2
2nd, technological process：
1st, check：
Kettle is clean, reactor, outer circulation pump and all valves of system, pipeline No leakage, vavuum pump normal operation, vacuum
Reach more than -0.098MPa, such as -0.099MPa, it is more low better.Supreme series-produced pure material in reactor, pipeline.
2nd, feed intake：
Put into BPA.
3rd, KOH is added：
KOH is added by inventory, can be pumped into and also directly pour into, first-class blind plate after KOH is added, negative pressure displacement 2 times is such as anti-
The good then negative pressure of kettle sealing is answered to feed.Plus start charging after KOH stirrings 40min.
Note：Slowly vacuum valve is driven during displacement, while observing visor, easily strip, shutoff valve is wanted after reactor outer circulation pipeline displacement
It is malleation in door, holding tube line.
4th, EO is entered：
Control system pressure is below 0.2MPa, first adds the 20% of the total consumptions of EO, system temperature is warming up into 150 DEG C,
System temperature is kept, remaining EO is added.
5th, cure, deaerate：
It is 150 DEG C to keep system temperature, cures 1h, and it is below 0.05MPa that kettle pressure is kept during curing, then controls the temperature to be
150 DEG C, it is below 0.05MPa, vacuum outgas 1h to keep kettle pressure.
6th, cooling plus antioxidant：
70-80 DEG C is cooled to, antioxidant T501 is added, stirring to antioxidant T501 is melted completely, blowing obtains a kind of double
Phenol A polyether products.
The index of bisphenol A polyether product is as follows obtained by the present embodiment：
Outward appearance is transparent slightly yellow liquid, and colourity is 21APHA, and pH is 6.3, and hydroxyl value is viscosity at 174mgKOH/g, 25 DEG C
For 1300CPS, water content is 0.017%.
Embodiment 3
A kind of preparation method of bisphenol A polyether, including：
First, each raw material dosage is as shown in table 3：
Each raw material dosage of bisphenol A polyether preparation method of 3 embodiment of the present invention of table 3
2nd, technological process：
1st, check：
Kettle is clean, reactor, outer circulation pump and all valves of system, pipeline No leakage, vavuum pump normal operation, vacuum
Reach more than -0.098MPa, such as -0.099MPa, it is more low better.Supreme series-produced pure material in reactor, pipeline.
2nd, feed intake：
Put into BPA.
3rd, KOH is added：
KOH is added by inventory, can be pumped into and also directly pour into, first-class blind plate after KOH is added, negative pressure displacement 2 times is such as anti-
The good then negative pressure of kettle sealing is answered to feed.Plus start charging after KOH stirrings 30min.
Note：Slowly vacuum valve is driven during displacement, while observing visor, easily strip, shutoff valve is wanted after reactor outer circulation pipeline displacement
It is malleation in door, holding tube line.
4th, EO is entered：
Control system pressure is below 0.2MPa, first adds the 10% of the total consumptions of EO, system temperature is warming up into 130 DEG C,
System temperature is kept, remaining EO is added.
5th, cure, deaerate：
It is 130 DEG C to keep system temperature, cures 1h, and it is below 0.05MPa that kettle pressure is kept during curing, then controls the temperature to be
130 DEG C, it is below 0.05MPa, vacuum outgas 1h to keep kettle pressure.
6th, cooling plus antioxidant：
70-80 DEG C is cooled to, BHT is added, stirring is melted completely to BHT, and blowing obtains a kind of bisphenol A polyether product.
The index of bisphenol A polyether product is as follows obtained by the present embodiment：
Outward appearance is transparent slightly yellow liquid, and colourity is 18APHA, and pH is 6.0, and hydroxyl value is viscosity at 166mgKOH/g, 25 DEG C
For 1500CPS, water content is 0.032%.
Embodiment 4
A kind of preparation method of bisphenol A polyether, including：
First, each raw material dosage is as shown in table 4：
Each raw material dosage of bisphenol A polyether preparation method of 4 embodiment of the present invention of table 4
2nd, technological process：
1st, check：
Kettle is clean, reactor, outer circulation pump and all valves of system, pipeline No leakage, vavuum pump normal operation, vacuum
Reach more than -0.098MPa, such as -0.099MPa, it is more low better.Supreme series-produced pure material in reactor, pipeline.
2nd, feed intake：
Put into BPA.
3rd, KOH is added：
KOH is added by inventory, can be pumped into and also directly pour into, first-class blind plate after KOH is added, negative pressure displacement 2 times is such as anti-
The good then negative pressure of kettle sealing is answered to feed.Plus start charging after KOH stirrings 30min.
Note：Slowly vacuum valve is driven during displacement, while observing visor, easily strip, shutoff valve is wanted after reactor outer circulation pipeline displacement
It is malleation in door, holding tube line.
4th, EO is entered：
Control system pressure is below 0.2MPa, first adds the 10% of the total consumptions of EO, system temperature is warming up into 140 DEG C,
System temperature is kept, remaining EO is added.
5th, cure, deaerate：
It is 140 DEG C to keep system temperature, cures 1h, and it is below 0.05MPa that kettle pressure is kept during curing, then controls the temperature to be
140 DEG C, it is below 0.05MPa, vacuum outgas 1h to keep kettle pressure.
6th, cooling plus antioxidant：
70-80 DEG C is cooled to, antioxidant T501 is added, stirring to antioxidant T501 is melted completely, blowing obtains a kind of double
Phenol A polyether products.
The index of bisphenol A polyether product is as follows obtained by the present embodiment：
Outward appearance is transparent slightly yellow liquid, and colourity is 16APHA, and pH is 5.6, and hydroxyl value is viscosity at 171mgKOH/g, 25 DEG C
For 1400CPS, water content is 0.026%.
Embodiment 5
A kind of preparation method of bisphenol A polyether, including：
First, each raw material dosage is as shown in table 5：
Each raw material dosage of bisphenol A polyether preparation method of 5 embodiment of the present invention of table 5
2nd, technological process：
1st, check：
Kettle is clean, reactor, outer circulation pump and all valves of system, pipeline No leakage, vavuum pump normal operation, vacuum
Reach more than -0.098MPa, such as -0.099MPa, it is more low better.Supreme series-produced pure material in reactor, pipeline.
2nd, feed intake：
Put into BPA.
3rd, KOH is added：
KOH is added by inventory, can be pumped into and also directly pour into, first-class blind plate after KOH is added, negative pressure displacement 2 times is such as anti-
The good then negative pressure of kettle sealing is answered to feed.Plus start charging after KOH stirrings 30min.
Note：Slowly vacuum valve is driven during displacement, while observing visor, easily strip, shutoff valve is wanted after reactor outer circulation pipeline displacement
It is malleation in door, holding tube line.
4th, EO is entered：
Control system pressure is below 0.2MPa, first adds the 10% of the total consumptions of EO, system temperature is warming up into 135 DEG C,
System temperature is kept, remaining EO is added.
5th, cure, deaerate：
It is 135 DEG C to keep system temperature, cures 1h, and it is below 0.05MPa that kettle pressure is kept during curing, then controls the temperature to be
135 DEG C, it is below 0.05MPa, vacuum outgas 1h to keep kettle pressure.
6th, cooling plus antioxidant：
70-80 DEG C is cooled to, BHT is added, stirring is melted completely to BHT, and blowing obtains a kind of bisphenol A polyether product.
The index of bisphenol A polyether product is as follows obtained by the present embodiment：
Outward appearance is transparent slightly yellow liquid, and colourity is 14APHA, and pH is 5.3, and hydroxyl value is viscosity at 177mgKOH/g, 25 DEG C
For 1250CPS, water content is 0.029%.
According to the inventive method, under pre-set level, each raw material dosage ratio used in adjustment can obtain different bis-phenols
A polyether products, gained bisphenol A polyether index is as follows：
Outward appearance is transparent slightly yellow liquid, and colourity is below 30APHA, and pH is 5-7, and hydroxyl value is 160-180mgKOH/g, 25
Viscosity is 1200-1600CPS at DEG C, and water content is below 0.5wt%.
In addition, existing bisphenol A polyether product must be stored in the shady and cool environment dried, under conditions of airtight package
Shelf-life is no more than 6 months, and the shelf-life of bisphenol A polyether product of the present invention under the same conditions can reach more than 1 year, this
Invention effectively increases the shelf-life of gained bisphenol A polyether product, can fully ensure that gained bisphenol A polyether product can be long-term
Stable retention properties, reduces in subsequent applications, because the production cycle is long, causes the situation of products obtained therefrom hydraulic performance decline.
Although illustrate and describing the present invention with specific embodiment, but it will be appreciated that various embodiments above is only used
To illustrate technical scheme, rather than its limitations；It will be understood by those within the art that：Without departing substantially from this hair
In the case of bright spirit and scope, the technical scheme described in foregoing embodiments can be modified, or to wherein
Some or all of technical characteristic carries out equivalent substitution；And these modifications or replacement, do not make the essence of appropriate technical solution
Depart from the scope of various embodiments of the present invention technical scheme；It is, therefore, intended that including belonging to the present invention in the following claims
In the range of all these substitutions and modifications.
Claims (10)
1. a kind of preparation method of bisphenol A polyether, it is characterised in that under vacuo, alkali is added into bisphenol-A, be sufficiently stirred for, plus
Enter epoxyalkane, cure, degassing adds antioxidant, obtains a kind of bisphenol A polyether product.
2. the preparation method of a kind of bisphenol A polyether according to claim 1, it is characterised in that the bisphenol-A and alkylene oxide
The mass ratio of hydrocarbon is 30-50：40-60, preferably 35-45：45-55, more preferably 42：50.
3. a kind of preparation method of bisphenol A polyether according to claim 1, it is characterised in that the vacuum of the vacuum
Reach more than -0.098MPa, preferably reach more than -0.099MPa.
4. the preparation method of a kind of bisphenol A polyether according to claim 1, it is characterised in that the alkali includes organic base
With the one or more in inorganic base, the one or more in inorganic strong alkali, more preferably KOH are preferably included；
Preferably, the consumption of the alkali is less than the 1% of the quality that always feeds intake of bisphenol-A and epoxyalkane, preferably 0.5%.
5. a kind of preparation method of bisphenol A polyether according to claim 1, it is characterised in that the time of the stirring is
More than 30min, preferably 40min.
6. the preparation method of a kind of bisphenol A polyether according to claim 1, it is characterised in that the epoxyalkane includes
One or more in C2-C6 epoxyalkane, preferably include the one or more in C2-C4 epoxyalkane, more preferably
Oxirane；
Preferably, the system pressure for adding epoxyalkane is controlled in below 0.2MPa；
Preferably, PART EPOXY alkane is first added, heats up afterwards, adds residual epoxide alkane；
It is further preferred that the PART EPOXY alkane be the total consumption of epoxyalkane less than 30%, preferably 10%-20% with
Under, more preferably 10%；
It is further preferred that the temperature of the heating is more than 120 DEG C, more preferably preferably 120-150 DEG C, 130-
140℃。
7. a kind of preparation method of bisphenol A polyether according to claim 1, it is characterised in that the system temperature of the curing
Degree control is preferably controlled in 120-150 DEG C more than 120 DEG C, and further preferably control is at 130-140 DEG C；
Preferably, the curing time is more than 1h, preferably 1h；
Preferably, control system pressure is below 0.5MPa during the curing；
Preferably, the temperature control of the degassing is preferably controlled in 120-150 DEG C more than 120 DEG C, and further preferably control exists
130-140℃；
Preferably, the time of the degassing is more than 1h, preferably 1h.
8. the preparation method of a kind of bisphenol A polyether according to claim 1, it is characterised in that the antioxidant includes virtue
One or more in fragrant amine antioxidants, Hinered phenols antioxidant and auxiliary antioxidant, preferably include no BHT antioxidant, answer
With antioxidant and without the one or more in amine environment-friendly type compound antioxidant；
Preferably, the consumption of the antioxidant is less than the 0.5% of the quality that always feeds intake of bisphenol-A and epoxyalkane, is preferably
0.2%；
Preferably, antioxidant is added after system is cooled；
It is further preferred that system temperature is cooled into 70-80 DEG C, antioxidant is added.
9. the preparation method of a kind of bisphenol A polyether according to claim 1, it is characterised in that carry out system after adding alkali
Vacuum is checked；
Preferably, add after antioxidant, stirring is fully melted to antioxidant, obtains a kind of bisphenol A polyether product.
10. the bisphenol A polyether production prepared using a kind of preparation method of any described bisphenol A polyethers of claim 1-9
Product.
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| CN111499501A (en) * | 2020-04-24 | 2020-08-07 | 浙江皇马科技股份有限公司 | Bisphenol A bis (2, 3-dihydroxypropyl) ether and preparation method thereof |
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| US20070282079A1 (en) * | 2006-05-31 | 2007-12-06 | Baker Hughes Incorporated | Alkoxylations in ketone solvents |
| US20100121111A1 (en) * | 2006-05-31 | 2010-05-13 | Baker Hughes Incorporated | Alkoxylations of High Melting Point Substrates in Ketone Solvents |
| CN104387247A (en) * | 2014-11-19 | 2015-03-04 | 浙江绿科安化学有限公司 | Method for preparing bis(hydroxyethyl) bisphenol A ether |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070282079A1 (en) * | 2006-05-31 | 2007-12-06 | Baker Hughes Incorporated | Alkoxylations in ketone solvents |
| US20100121111A1 (en) * | 2006-05-31 | 2010-05-13 | Baker Hughes Incorporated | Alkoxylations of High Melting Point Substrates in Ketone Solvents |
| US20140142345A1 (en) * | 2006-05-31 | 2014-05-22 | Baker Hughes Incorporated | Alkoxylation of crude bisphenol a |
| CN104387247A (en) * | 2014-11-19 | 2015-03-04 | 浙江绿科安化学有限公司 | Method for preparing bis(hydroxyethyl) bisphenol A ether |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111499501A (en) * | 2020-04-24 | 2020-08-07 | 浙江皇马科技股份有限公司 | Bisphenol A bis (2, 3-dihydroxypropyl) ether and preparation method thereof |
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