CN110423339A - A kind of water soluble polyether polyols, polyurethane foam and preparation method thereof - Google Patents
A kind of water soluble polyether polyols, polyurethane foam and preparation method thereof Download PDFInfo
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- CN110423339A CN110423339A CN201910788618.1A CN201910788618A CN110423339A CN 110423339 A CN110423339 A CN 110423339A CN 201910788618 A CN201910788618 A CN 201910788618A CN 110423339 A CN110423339 A CN 110423339A
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- polyether polyols
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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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
- C08G65/2609—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 aliphatic 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
- C08G65/2642—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 catalyst used
- C08G65/2669—Non-metals or compounds thereof
- C08G65/2672—Nitrogen or compounds thereof
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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
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
This application involves a kind of methods for preparing water soluble polyether polyols, it includes under 80~160 DEG C of reaction temperature and in the case where reaction pressure is no more than 0.60Mpa, so that polyether polyol synthesis initiator liquid sorbitol and epoxide is reacted predetermined amount of time under the catalysis of tertiary amine catalyst, obtains the water soluble polyether polyols.The application further relates to a kind of water soluble polyether polyols prepared by method as described above.The application further relates to a kind of polyurethane foam prepared using water soluble polyether polyols as described above.Water soluble polyether polyols preparation method as described herein improves the yield of water soluble polyether polyols, and shortens the production cycle, and polyether polyol obtained is soluble easily in water, and degree of functionality is high, and activity is high, and hydroxyl value and viscosity are adjustable, and stability is preferable.In addition, good stability of the dimension excellent using the polyurethane rigid foam plastic mechanical performance of the polyether polyols alcohol production of methods described herein preparation.
Description
Technical field
This application involves technical field of chemical synthesis, and in particular to a kind of water soluble polyether polyols, the water soluble polyether
The preparation method of polyalcohol and the polyurethane foam made of the water soluble polyether polyols.Polyurethane foam as described herein
It may be used on the industries such as heat preservation plate material, pipe insulation, refrigerator, refrigerator-freezer and cold chain.
Background technique
Polyurethane foam plastics is made of the aggregated foaming of polyisocyanates and hydroxy compounds, passes through feed change type
And composition, it can significantly change product form and its performance, obtain the polyurethane foam plastics product from soft to hard.
Polyurethane rigid foam plastic has good physical mechanical property, acoustical behavior and chemical-resistance, especially has lower
Thermal coefficient, so being widely used in the various field of thermal insulation such as household electrical appliances, building board, pipeline, external wall spraying.
In the preparation of polyurethane rigid foam plastic, degree of functionality, the activity of polyether polyol are improved, poly- ammonia can be improved
The mechanical property and processing performance of ester product.Traditional polyether polyol using the cooperative compositions such as such as ethylene glycol, propylene glycol as
Initiator synthesizes.The production cycle of this polyether polyol preparation is long, and the polyurethane rigid foam plastic prepared is easily opened
It splits, form that bad, finish is not high, mechanical performance is bad, poor dimensional stability etc..
For this purpose, there is an urgent need in the art to a kind of high functionality for preparing rigid foam, the higher water soluble polyether of activity are more
First alcohol, and the production cycle is shorter, cost is relatively low.
Summary of the invention
The application's is designed to provide a kind of method for preparing water soluble polyether polyols.Specifically, described herein
Method by using high functionality liquid sorbitol as polyether polyol synthesize initiator, and use specific tertiary amines
Catalyst carrys out the reaction between catalyzing sorbitol and epoxide, finally obtains high functionality, the higher water-soluble poly of activity
Ethoxylated polyhydric alcohol.
The purpose of the application, which also resides in, provides a kind of water soluble polyether polyols prepared by method as described above.
The purpose of the application, which also resides in, provides a kind of combined polyether by containing water soluble polyether polyols as described above
Manufactured polyurethane foam is reacted with isocyanates.
In order to solve the above-mentioned technical problem, the application provides following technical scheme.
In the first aspect, the application provides a kind of method for preparing water soluble polyether polyols, which is characterized in that described
Method includes under 80~160 DEG C of reaction temperature and reaction pressure is in the case where being no more than 0.60Mpa, makes polyether polyol
Synthesis initiator liquid sorbitol and epoxide react predetermined amount of time under the catalysis of tertiary amine catalyst, obtain described
Water soluble polyether polyols.
In a kind of embodiment of first aspect, the liquid sorbitol be VC grades of sorbierites, food-grade sorbierite and
One or more of daily use chemicals grade sorbierite, and counted on the basis of the quality of dry matter, the content of the liquid sorbitol is greater than
Or it is equal to 50%.
In a kind of embodiment of first aspect, the tertiary amine catalyst is Dodecyl Dimethyl Amine, 14
One or more of alkyl dimethyl tertiary amide, hexadecyldimethyl benzyl ammonium tertiary amine and octadecyldimethyl tertiary amine.
In a kind of embodiment of first aspect, initiator, the epoxide are synthesized with the polyether polyol
It is counted on the basis of the gross mass of the catalyst, the mass percent of the catalyst is 0.2%-5.5%.
In a kind of embodiment of first aspect, the epoxide includes ethylene oxide, propylene oxide or ring
One or more of oxygen chloropropane.
In a kind of embodiment of first aspect, the method includes the following steps:
S1: the polyether polyol synthesis initiator and the catalyst are mixed under negative pressure, and is heated to 100~150
Vacuum dehydration at DEG C obtains the first reaction mixture；
S2: under 80~160 DEG C of reaction temperature, the epoxide and described first for mixing first part are mixed
Close object and simultaneously react the first predetermined amount of time, obtain the second reaction mixture, wherein first part's epoxide account for it is described
The 5-20% of epoxide total amount；
S3: it is added described in second part in a manner of continuous charging or batch charging into second reaction mixture
Epoxide, it is second predetermined that the reaction was continued under 100~160 DEG C of reaction temperatures and no more than the reaction pressure of 0.60MPa
Period obtains third reaction mixture；
S4: curing the third reaction mixture in 100~160 DEG C of range of reaction temperature, until pressure
Until no longer changing, the water soluble polyether polyols are obtained.
In a kind of embodiment of first aspect, step S1 includes that the polyether polyol is synthesized initiator and described
After catalyst is separately added into reaction kettle mixing, it is passed through inert gas and by positive pressure negative pressure alternating permutation at least twice to guarantee body
The anhydrous and oxygen-free reaction condition of system.
In a kind of embodiment of first aspect, the epoxide of the first part is before charging in step sl
It is dripped in advance, is further continued for adding the epoxide of the second part when temperature rises and pressure declines.
In a kind of embodiment of first aspect, the curing of step S4 includes the temperature range at 100~130 DEG C
Interior curing third predetermined amount of time, and the 4th predetermined amount of time is then cured within the temperature range of 130~160 DEG C.
In second aspect, the application provides a kind of by the water soluble polyether polyols of preparing as described in relation to the first aspect
Water soluble polyether polyols prepared by method.
In a third aspect, the application provides a kind of polyurethane foam, and the polyurethane foam is by the inclusion of such as second party
The combined polyether of water soluble polyether polyols described in face and isocyanates react to prepare.
Compared with prior art, the good effect of the application is (1) water soluble polyether polyols preparation as described herein
Method improves the yield of water soluble polyether polyols, and shortens the production cycle；
(2) water soluble polyether polyols preparation method step as described herein is simple, and technological operation is simple, production cost
It is low, and polyether polyol obtained is soluble easily in water, degree of functionality is high, and activity is high, and hydroxyl value and viscosity are adjustable, and stability is preferable, can
Meet different customer requirements；
(3) the polyurethane rigid foam plastic mechanical performance of the polyether polyols alcohol production prepared with methods described herein is excellent
It is different, good stability of the dimension.
Specific embodiment
Unless otherwise indicated, from context cues or belong to the convention of the prior art, otherwise number all in the application
It is all based on weight with percentage, and test and characterizing method used is all synchronous with the submission date of the application.It is being applicable in
In the case where, any patent, patent application or disclosure involved in the application are fully incorporated in this as reference, and its
Patent families of equal value are also introduced into as reference, about the synthetic technology in this field, product disclosed by these special documents
With the definition of fabrication design, polymer, comonomer, initiator or catalyst etc..If the specific art disclosed in the prior art
Defining for language is inconsistent with any definition provided herein, then term provided herein of being subject to defines.
Digital scope in the application is approximation, therefore unless otherwise stated, it may include the number other than range
Value.Numberical range include with the increased all numerical value from lower limit value to upper limit value of 1 unit, condition be any lower value with
There are the intervals of at least two unit between any high value.For example, if compositional, physics or other property (such as molecules
Amount, melt index (MI) etc.) it is 100 to 1000, it is meant that clearly list all single numbers, such as 100,101,102 etc., with
And all subranges, such as 100 to 166,155 to 170,198 to 200 etc..For comprising the numerical value less than 1 or comprising big
In the range of 1 score (such as 1.1,1.5 etc.), then suitably regard 1 unit as 0.0001,0.001,0.01 or 0.1.
For the range comprising the units less than 10 (such as 1 to 5), usually regard 1 unit as 0.1.These are only intended to table
The specific example of the content reached, and all possible combination of the numerical value between cited minimum and peak is all recognized
In this application for clear record.It is also pointed out that term " first " herein, " second " etc. do not limit sequencing, only
In order to distinguish the substance of different structure.
About chemical compound in use, unless explicitly stated otherwise, otherwise odd number includes all isomeric forms, otherwise also
So (for example, whole isomers that " hexane " either individually or collectively includes hexane).In addition, unless explicitly stated otherwise, otherwise using
"one", the noun that "an" or "the" are described also includes its plural form.
Term "comprising", " comprising ", " having " and their derivative are not excluded for any other component, step or mistake
The presence of journey, and whether disclose in this application with these other components, step or process unrelated.To eliminate any query,
Unless expressly stated, otherwise in the application it is all use term "comprising"s, " comprising ", or " having " composition may include appoint
What additional additive, auxiliary material or compound.On the contrary, in addition to necessary to operating characteristics those, term " substantially by ...
Composition " excludes any other component, step or process except the hereinafter described range of any term.Term " by ...
Composition " does not include any component, step or the process for not specifically describing or listing.Unless expressly stated, otherwise term "or" refers to
Separate member listed or any combination thereof.
In a specific embodiment, the application provides a kind of method for preparing water soluble polyether polyols, the side
Method includes the following steps: under 80~160 DEG C of reaction temperature and reaction pressure is in the case where being no more than 0.60Mpa, makes water
Dissolubility polyether polyol synthesis initiator liquid sorbitol and epoxide react predetermined amount of time under the catalysis of catalyst,
Obtain the water soluble polyether polyols.In a kind of special specific embodiment, rigid foam water-soluble poly of the invention
The preparation method of ethoxylated polyhydric alcohol, being included in reaction temperature is 80~160 DEG C, and reaction pressure is no more than under conditions of 0.60Mpa, to
It is gradually passed through propylene oxide in water soluble polyether polyols initiator and water soluble polyether polyols catalyst for synthesizing, makes its hair
Raw ring-opening polymerization, is made the water soluble polyether polyols；Wherein water soluble polyether polyols initiator is liquid sorbitol.
In one embodiment, the water soluble polyether polyols synthesis initiator is liquid sorbitol.It can be used for this
The liquid sorbitol of the preparation method of application includes the liquid sorbitol of all different contents.In a specific embodiment,
Liquid sorbitol includes one or more of VC grades of sorbierites, food-grade sorbierite and daily use chemicals grade sorbierite.A kind of special
It in specific embodiment, is counted on the basis of the quality of dry matter, food-class liquid sorbierite is yellowish or colorless and transparent viscous
Thick liquid, sorbitol content 70-78%.In a kind of special specific embodiment, on the basis of the quality of dry matter
Meter, daily use chemicals grade liquid sorbitol are yellowish or colorless transparent viscous liquid, sorbitol content 50-55%.In a kind of spy
It in other specific embodiment, is counted on the basis of the quality of dry matter, VC grades of liquid sorbitols are yellowish or colorless and transparent viscous
Thick liquid, sorbitol content are greater than or equal to 70%.
In one embodiment, the catalyst can be tertiary amine catalyst.In a specific embodiment, described
Tertiary amine catalyst can be Dodecyl Dimethyl Amine, dodecyldimethylamine base tertiary amine, hexadecyldimethyl benzyl ammonium tertiary amine and ten
One or more of eight alkyl dimethyl tertiary amides
In one embodiment, with the total of water soluble polyether polyols synthesis initiator, epoxide and catalyst
It is counted on the basis of quality, the mass percent of catalyst is 0.2%-5.5%.
In one embodiment, the epoxide includes ethylene oxide and/or propylene oxide.
In one embodiment, the method includes the following steps:
After the water soluble polyether polyols are synthesized initiator and catalyst addition reaction kettle mixing, open under negative pressure
Stirring, and it is heated to 100~150 DEG C of vacuum dehydrations；
The reaction kettle is added in epoxide described in first part, and controlling reaction temperature is 80~160 DEG C, is caused
Reaction, wherein first part's epoxide accounts for the 5-20% of the epoxide total amount；
The epoxide of second part is added in a manner of continuous charging or batch charging, at 100~160 DEG C
Polymerization reaction occurs under reaction pressure no more than 0.60MPa for temperature；
Maintaining reaction temperature is cured in 100~160 DEG C of range, until pressure no longer changes.
In one embodiment, the water soluble polyether polyols are synthesized into initiator and catalyst is separately added into reaction
After kettle mixing, it is passed through inert gas and by positive/negative-pressure alternating permutation at least twice to guarantee that the anhydrous and oxygen-free of reaction system reacts
Condition.
In one embodiment, first part's epoxide is dripped in advance before charging, when temperature rises, pressure
Power is further continued for adding the second part epoxide when declining.
In one embodiment, the maturing process is divided into two parts, and the temperature control of 2 hours or so early period of curing exists
In the range of 100~130 DEG C, the temperature of curing in the later period 2 hours or so is controlled in the range of 130~160 DEG C.
In some embodiments, the preparation method of water soluble polyether polyols carries out as steps described below:
(1) reaction kettle is added in water soluble polyether polyols initiator and water soluble polyether polyols catalyst for synthesizing
Afterwards, it is lower unlatching stirring in negative pressure, and is heated to 80~160 DEG C；
(2) pause heating, first part's epoxide is rapidly joined into reaction kettle, and control reaction temperature be 80~
160 DEG C, wherein first part's epoxide accounts for the 5-20% of epoxide total amount；
(3) second part epoxide is added in a manner of continuous charging or batch charging, in 100~160 DEG C of temperature
It spends, polymerization reaction occurs under the reaction pressure no more than 0.60MPa, wherein when using batch charging, the feeding quantity of every batch of
It is the 6%~10% of propylene oxide total amount；
(4) maintaining reaction temperature is cured in 100~160 DEG C of range, until pressure not until variation；
In a preferable embodiment, the method for preparing water soluble polyether polyols may include following steps:
(1) water soluble polyether polyols are synthesized into initiator and accounts for the catalyst of reactant gross mass 0.5%-2.5%
It is added in reaction vessel, twice, finally, under negative pressure condition, unlatching is heated with stirring to 80~160 to negative pressure positive pressure alternating permutation
DEG C, after reaching 90 DEG C or so, stops heating, start into propylene oxide；
(2) it is dripped in advance before propylene oxide feed, pause charging, observing response after pressure is reached for positive pressure in reaction kettle
Situation shows that material starts to react when temperature rises and pressure declines, is further continued for into propylene oxide, controlled at 100-160
℃；
(3) after temperature reaches 90 DEG C, continue slowly to feed early period, heat up using reaction heat into propylene oxide, control
Reaction temperature at this time about 5 hours of propylene oxide feed, opens outer circulation pump, uses object as far as possible at 90~160 DEG C after charging
The reaction heat of material makes reaction system heat up, and does not have to heating, prevents hot-spot, lead to color depth, during this material reaction, pressure
It is no more than 0.60MPa by force；
(4) maintaining reaction temperature is cured, and until pressure not until variation, during this, 2 hours or so early period is ripe
Change temperature control within the scope of 90~130 DEG C, curing temperature control in the later period 2 hours or so is within the scope of 130~150 DEG C, finally
After reaching qualification, cool down blowing.
In another embodiment specific implementation mode, the application provides a kind of polynary by preparing water soluble polyether as described above
Water soluble polyether polyols prepared by the method for alcohol.
In another embodiment specific implementation mode, the application provides a kind of polyurethane foam, by the inclusion of as described above
It is prepared by reaction between water soluble polyether polyols and isocyanates.It is described poly- in a kind of special specific embodiment
Urethane foam is hard polyurethane foams.
The hard polyurethane foam of the rigid foam water soluble polyether polyols production prepared using the present processes is moulded
Expect that mechanical performance is strong, good stability of the dimension.
Reagent and raw material used herein are commercially available.
Embodiment
Below in conjunction with embodiments herein, clear and complete description is carried out to the technical solution of the application.Such as nothing
It illustrates, reagent used and raw material can all be bought by commercial sources.Actual conditions are not specified in the following example
Experimental method according to conventional methods and conditions, or is selected according to product manual.
The application is further described by the following examples, embodiment is raw materials used as follows:
Test and measuring method:
OH.V value: it is measured according to the method for DIN53240.
Viscosity: generally dynamic viscosity is measured using rotational viscometer according to the method for DIN53019, measuring temperature 25
℃。
Embodiment 1
2L reaction kettle is added in liquid sorbitol (VC grades of liquid sorbitols, sorbitol content 70%, moisture 30%) 130g
In, adding 20g Dodecyl Dimethyl Amine catalyst, negative pressure and positive pressure alternating permutation be in negative pressure twice, finally-
In the case of 0.090MPa, stirring is opened, warming while stirring is to 90 DEG C.Replacement process includes that reaction kettle is pressurized to 0.15MPa,
Row pressure is repeated once to 0MPa.Then, reaction kettle is pressurized to 0.10MPa.Opening vacuum, to be extracted into negative pressure minimum, is repeated once.So
Afterwards, vacuum dehydration 2 hours.Then 40g propylene oxide is added in reaction kettle for then pause heating.Before propylene oxide feed
It is dripped in advance, pause charging, observing response situation, temperature rise after pressure is reached for positive pressure in reaction kettle, when pressure declines
Illustrate that material starts to react, is further continued for into propylene oxide 640g, concrete operations are as follows: controlled at 90-100 DEG C, working as temperature
After reaching 90 DEG C, continue to add propylene oxide, slowly feed early period, heated up using reaction heat, control reaction temperature 100~
160℃.About 5 hours of propylene oxide feed at this time.Outer circulation pump is opened after charging.The reaction heat liter of material is utilized as far as possible
Temperature does not have to heating, prevents hot-spot, lead to reaction mass color depth.During this material reaction, pressure is no more than 0.60MPa.
Maintaining reaction temperature is cured, until pressure does not change, during this, and 2 hours or so early period of curing temperature control
For system within the scope of 100~130 DEG C, curing temperature control in the later period 2 hours or so finally reaches qualification within the scope of 130~160 DEG C
Afterwards, cool down blowing.The overall manufacturing period is 9.0 hours, which includes replacement process after feeding intake, propylene oxide
Elicitation procedure, the maturing process after the fill process of propylene oxide, and charging, until blowing terminates.
Embodiment 2
By liquid sorbitol (daily use chemicals grade liquid sorbitol, sorbitol content 50%, solid content 70%, moisture 30%) 240g
It is added in reaction kettle, adds 12g dodecyldimethylamine base tertiary amine catalyst, negative pressure and positive pressure alternating permutation twice, finally exist
In the case of negative pressure is -0.090MPa, stirring is opened, warming while stirring is to 90 DEG C.Replacement process includes being pressurized to reaction kettle
0.15MPa, row pressure to 0MPa, is repeated once.Then, reaction kettle is pressurized to 0.10MPa.Open vacuum minimum, the weight that is extracted into negative pressure
It is multiple primary.Then, vacuum dehydration 3 hours, pause heating, then 40g propylene oxide is added in reaction kettle.When propylene oxide into
It is dripped in advance before material, pause charging, observing response situation, temperature rise after pressure is reached for positive pressure in reaction kettle, under pressure
Illustrate that material starts to react when drop, is further continued for into propylene oxide 640g.Concrete operations are as follows: controlled at 90-100 DEG C, when
After temperature reaches 90 DEG C, continue to add propylene oxide, slowly feed early period, heated up using reaction heat, control reaction temperature exists
100~160 DEG C.About 5 hours of propylene oxide feed at this time.Outer circulation pump is opened after charging.The reaction of material is used as far as possible
Heat heating, does not have to heating, prevents hot-spot, lead to color depth.During this material reaction, pressure is no more than 0.60MPa.It maintains
Reaction temperature is cured, and until pressure does not change, during this, the control of 2 hours or so early period of curing temperature exists
Within the scope of 100~130 DEG C, curing temperature control in the later period 2 hours or so is within the scope of 130~160 DEG C, after finally reaching qualification,
Cool down blowing.The overall manufacturing period is 9.5 hours.
Embodiment 3
Liquid sorbitol (VC grades of liquid sorbitols, sorbitol content 70%, moisture 30%) 240g is added in reaction kettle,
Adding 12g hexadecyldimethyl benzyl ammonium tertiary amine catalyst, negative pressure and positive pressure alternating permutation be in negative pressure twice, finally-
In the case of 0.090MPa, stirring is opened, warming while stirring is to 90 DEG C.Replacement process includes that reaction kettle is pressurized to 0.15MPa,
Row pressure is repeated once to 0MPa.Then, reaction kettle is pressurized to 0.10MPa.Opening vacuum, to be extracted into negative pressure minimum, is repeated once.So
Afterwards, it opens vacuum dehydration 3 hours, suspends heating after dehydration, then 50g propylene oxide is added in reaction kettle.When propylene oxide into
It is dripped in advance before material, pause charging, observing response situation, temperature rise after pressure is reached for positive pressure in reaction kettle, under pressure
Illustrate that material starts to react when drop, is further continued for into propylene oxide 700g.Concrete operations are as follows: controlled at 90-100 DEG C.When
After temperature reaches 90 DEG C, continue to add propylene oxide, slowly feed early period, heated up using reaction heat, control reaction temperature exists
90~150 DEG C.About 5 hours of propylene oxide feed at this time.Outer circulation pump is opened after charging.The reaction heat of material is used as far as possible
Heating does not have to heating, prevents hot-spot, lead to color depth.During this material reaction, pressure is no more than 0.60MPa.Remain anti-
Temperature is answered to be cured, until pressure does not change, during this, 2 hours or so early period of curing temperature is controlled 90
Within the scope of~130 DEG C, curing temperature control in the later period 2 hours or so is within the scope of 130~150 DEG C, after finally reaching qualification, cooling
Blowing.The overall manufacturing period is 9 hours.
Comparative example 1
Liquid sorbitol 240g is added in reaction kettle, 2.5gKOH catalyst, negative pressure and positive pressure alternating permutation two are added
It is secondary, finally when negative pressure is -0.090MPa, stirring is opened, warming while stirring opens vacuum dehydration 3 hours, temporarily to 90 DEG C
Stop heating, then 50g propylene oxide is added in reaction kettle.It is dripped in advance before propylene oxide feed, when pressure in reaction kettle
Suspend charging, observing response situation after being reached for positive pressure, temperature rises, and pressure illustrates that material starts to react when declining, and is further continued for
Into propylene oxide 700g, concrete operations are as follows: controlled at 90-100 DEG C.After temperature reaches 90 DEG C, continue to add 700g
Propylene oxide, early period slowly feed, and are heated up using reaction heat, control reaction temperature at 90~150 DEG C.At this time propylene oxide into
Expect about 5 hours.Outer circulation pump is opened after charging.It is heated up as far as possible with the reaction heat of material, does not have to heating, prevent local mistake
Heat leads to color depth.During this material reaction, pressure is no more than 0.60MPa.Maintaining reaction temperature is cured, until pressure
Until not changing, during this, 2 hours or so early period of curing temperature is controlled within the scope of 90~130 DEG C, and the later period 2 hours
Left and right curing temperature control within the scope of 130~150 DEG C, after finally reaching qualification, cooling liquid relief post-processing, remove metal from
Son.Time about 8 hours, the overall manufacturing period was 18 hours.
Test result arranges such as table 1:
The polyether polyol raw material proportioning and performance parameter of table 1 embodiment 1-3 and comparative example 1
Effect example
Polyether polyol prepared by above-described embodiment and comparative example is configured to combined polyether, specific formula is as follows:
Foaming process: take said combination polyether polyol and isocyanates PAPI using low-pressure blowing machine with the stream of 30g/s
Amount carries out material feeding, and the mass ratio of combined polyether glycol and PAPI are 1:1.03, and poly- ammonia is made in 25 DEG C of at a temperature of foaming
Ester foam.
The performance of measurement gained polyurethane foam, testing standard are as follows respectively:
Compressive strength is measured according to standard GB/T/T8812 88；
Shrinking percentage is measured according to standard GB/T/T8811 88.
Gained polyurethane foam performance data are as shown in table 2 below:
Table 2: the combined polyether of embodiment and comparative example and the results of property of polyurethane foam
From above-mentioned experimental data it is found that the compression of the polyurethane foam prepared using the water soluble polyether polyols of the application
Intensity and shrinking percentage are superior to the polyurethane foam prepared using the polyether polyol of comparative example.
The above-mentioned description to embodiment is that this Shen can be understood and applied for the ease of those skilled in the art
Please.Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein
General Principle is applied in other embodiments without paying creative labor.Therefore, the application is not limited to implementation here
Example, those skilled in the art make according to herein disclosed content in the case where not departing from the application scope and spirit
It improves and modifies within all scope of the present application.
Claims (10)
1. a kind of method for preparing water soluble polyether polyols, which is characterized in that the method includes in 80~160 DEG C of reaction
At a temperature of and in the case where reaction pressure is no more than 0.60Mpa, make polyether polyol synthesis initiator liquid sorbitol and ring
Oxygen compound reacts predetermined amount of time under the catalysis of tertiary amine catalyst, obtains the water soluble polyether polyols.
2. the method for preparing water soluble polyether polyols as described in claim 1, which is characterized in that the liquid sorbitol is
One or more of VC grades of sorbierites, food-grade sorbierite and daily use chemicals grade sorbierite, and counted on the basis of the quality of dry matter,
The content of the liquid sorbitol is greater than or equal to 50%.
3. the method for preparing water soluble polyether polyols as described in claim 1, which is characterized in that the tertiary amine catalyst
For Dodecyl Dimethyl Amine, dodecyldimethylamine base tertiary amine, hexadecyldimethyl benzyl ammonium tertiary amine and octadecyldimethyl uncle
One or more of amine.
4. the method for preparing water soluble polyether polyols as described in claim 1, which is characterized in that with the polyether polyol
It is counted on the basis of the gross mass of synthesis initiator, the epoxide and the catalyst, the mass percent of the catalyst
For 0.2%-5.5%.
5. the method for preparing water soluble polyether polyols as described in claim 1, which is characterized in that the epoxide packet
Include one or more of ethylene oxide, propylene oxide or epoxychloropropane.
6. the method for preparing water soluble polyether polyols as described in claim 1, which is characterized in that the method includes following
Step:
S1: the polyether polyol synthesis initiator and the catalyst are mixed under negative pressure, and is heated at 100~150 DEG C
Vacuum dehydration obtains the first reaction mixture；
S2: under 80~160 DEG C of reaction temperature, the epoxide and first mixture of first part are mixed
And the first predetermined amount of time is reacted, the second reaction mixture is obtained, wherein first part's epoxide accounts for the epoxy
The 5-20% of total amount of compound；
S3: the epoxy of second part is added into second reaction mixture in a manner of continuous charging or batch charging
Compound, the reaction was continued the second predetermined time under 100~160 DEG C of reaction temperatures and reaction pressure no more than 0.60MPa
Section, obtains third reaction mixture；
S4: curing the third reaction mixture in 100~160 DEG C of range of reaction temperature, until pressure is no longer
Until variation, the water soluble polyether polyols are obtained.
7. the method for preparing water soluble polyether polyols as claimed in claim 6, which is characterized in that step S1 includes will be described
After polyether polyol synthesis initiator and the catalyst are separately added into reaction kettle mixing, it is passed through inert gas and is born by positive pressure
Press alternating permutation at least twice with the anhydrous and oxygen-free reaction condition of guarantee system.
8. the method for preparing water soluble polyether polyols as claimed in claim 6, which is characterized in that in step sl described the
The epoxide of a part is dripped in advance before charging, is further continued for adding described second when temperature rises and pressure declines
The epoxide divided；
And/or the curing of step S4 be included in 100~130 DEG C within the temperature range of cure third predetermined amount of time, and
The 4th predetermined amount of time is then cured within the temperature range of 130~160 DEG C.
9. a kind of pass through the water as prepared by the method for any of claims 1-8 for preparing water soluble polyether polyols
Dissolubility polyether polyol.
10. a kind of polyurethane foam, which is characterized in that the polyurethane foam is by the inclusion of as claimed in claim 9 water-soluble
The combined polyether of property polyether polyol and isocyanates react to prepare.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113698587A (en) * | 2021-09-08 | 2021-11-26 | 航锦科技股份有限公司 | Preparation method of hard foam polyether polyol |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1995088A (en) * | 2006-12-19 | 2007-07-11 | 中国石油化工股份有限公司 | Method for preparing temperature-resistant hard polyurethane foam |
| US20120004334A1 (en) * | 2009-03-24 | 2012-01-05 | Dow Global Technologies Llc | Production of rigid polyurethane foams and the use thereof |
| EP2677030A1 (en) * | 2012-06-21 | 2013-12-25 | Latvijas Valsts Koksnes kimijas instituts | Polyurethane rigid and flexible foams as composite obtained from wood origin raw materials and used as support for immobilization of microorganisms that produce ligninolytic enzymes |
| CN104672426A (en) * | 2015-03-24 | 2015-06-03 | 合肥华凌股份有限公司 | Polyurethane composition, polyurethane foam as well as manufacture method thereof and fridge |
| CN106810682A (en) * | 2017-01-23 | 2017-06-09 | 山东诺威新材料有限公司 | The preparation method of rigid-foam polyether polyol |
| CN108047442A (en) * | 2017-12-20 | 2018-05-18 | 上海东大化学有限公司 | A kind of compound polyether polyol of rigid foam and preparation method thereof |
| CN109762158A (en) * | 2018-12-14 | 2019-05-17 | 上海东大化学有限公司 | A kind of polyether polyol and preparation method thereof |
| CN110117358A (en) * | 2019-05-17 | 2019-08-13 | 万华化学集团股份有限公司 | High functionality polyether polyol and its preparation method and application |
-
2019
- 2019-08-26 CN CN201910788618.1A patent/CN110423339A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1995088A (en) * | 2006-12-19 | 2007-07-11 | 中国石油化工股份有限公司 | Method for preparing temperature-resistant hard polyurethane foam |
| US20120004334A1 (en) * | 2009-03-24 | 2012-01-05 | Dow Global Technologies Llc | Production of rigid polyurethane foams and the use thereof |
| EP2677030A1 (en) * | 2012-06-21 | 2013-12-25 | Latvijas Valsts Koksnes kimijas instituts | Polyurethane rigid and flexible foams as composite obtained from wood origin raw materials and used as support for immobilization of microorganisms that produce ligninolytic enzymes |
| CN104672426A (en) * | 2015-03-24 | 2015-06-03 | 合肥华凌股份有限公司 | Polyurethane composition, polyurethane foam as well as manufacture method thereof and fridge |
| CN106810682A (en) * | 2017-01-23 | 2017-06-09 | 山东诺威新材料有限公司 | The preparation method of rigid-foam polyether polyol |
| CN108047442A (en) * | 2017-12-20 | 2018-05-18 | 上海东大化学有限公司 | A kind of compound polyether polyol of rigid foam and preparation method thereof |
| CN109762158A (en) * | 2018-12-14 | 2019-05-17 | 上海东大化学有限公司 | A kind of polyether polyol and preparation method thereof |
| CN110117358A (en) * | 2019-05-17 | 2019-08-13 | 万华化学集团股份有限公司 | High functionality polyether polyol and its preparation method and application |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113698587A (en) * | 2021-09-08 | 2021-11-26 | 航锦科技股份有限公司 | Preparation method of hard foam polyether polyol |
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Application publication date: 20191108 |