CN109627434A - A kind of preparation method of inorganic modified polyether polyol - Google Patents
A kind of preparation method of inorganic modified polyether polyol Download PDFInfo
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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
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33396—Polymers modified by chemical after-treatment with organic compounds containing nitrogen having oxygen in addition to nitrogen
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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
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
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Abstract
The present invention relates to a kind of preparation methods of inorganic modified polyether polyol comprising the steps of: is reacted with basic polyether polyalcohol with organic acid containing tertiary amine and its derivative under the action of catalyst first, prepares based polyether polyol containing tertiary amine；Then it will contain tertiary amine based polyether polyol to react with halogenated alkane, and prepare quaternary dispersing agent；Finally by inorganic powder material, it is scattered in basic polyether under the effect of quaternary dispersing agent, inorganic modified polyether polyol is finally made.Prepared polyether polyol has the characteristics such as odorlessness, lower cost, preferable stability.
Description
Technical field
The present invention relates to a kind of novel inorganic modified polyether polyol preparation methods, specifically prepare a kind of novel
Stabilizer, and as raw material prepare a kind of odorlessness, low cost inorganic modified polyether polyol preparation method.
Background technique
Traditional polymer polyatomic alcohol is also referred to as polymer scion grafting polyether polyol, is polyurethane foam plastics polyalcohol
One important species originally develops polymer polyatomic alcohol and is mainly based upon in soft bubble formula using to promote foamed plastics carrying
Performance, but its cost also can be promoted accordingly for soft bubble polyethers.
The main reason for addition polymer polyatomic alcohol promotes foamed plastics bearing capacity is that polymer polyatomic alcohol is deposited
Admittedly containing, therefore improving the solid containing the support performance that can effectively promote polymer polyatomic alcohol of polymer polyatomic alcohol.
But there are problems that a comparison is difficult to thoroughly solve in polymer polyatomic alcohol preparation process: can generate and make us not
Pleasant smell.To find out its cause, mainly in synthesis process radical initiator decomposition product, however use polymer polyatomic alcohol
The product of production applies the every aspect in people's life, so being highly desirable to reduce or remove in polymer polyatomic alcohol
Smell.The smell issued from elimination initiator and its product is needed, to solve the problems, such as polymer polyatomic alcohol smell.
Chinese patent CN105461913A disclose it is a kind of disperse element silicon in polyethers, prepare Si modification polyalcohol
Method.The product bulky grain of preparation is more, easily settled, and requires in reaction process mixed effect stringenter.
For another described in patent CN03811632.4, modified Phthalic Anhydride produces macromonomer, phthalic anhydride and macromolecular polyethers system
Standby phthalic anhydride half ester prepares a kind of macromonomer, then is reacted with styrene and acrylonitrile, prepares polymer polyatomic alcohol, exists
The problems such as smell is high, cost advantage is unobvious.Above-mentioned technique is still response type and is modified, and certainly exists smell problem, this
Powerful post-processing engineering is needed, preparation cost is increased.Polymer polyatomic alcohol is prepared in a conventional manner, equally exists viscosity control
Make unstable, the larger problem of smell.
Aiming at the problem that prior art polymer polyatomic alcohol smell present in, a kind of new polymer polyatomic alcohol of demand
Preparation method can be used in preparing the polymer polyatomic alcohol of low smell.
Summary of the invention
The present invention provides a kind of preparation method of inorganic modified polyether polyol, and obtained modified polyether polylol has low
The feature of smell low cost, and there is preferable stability.And prepared inorganic modified polyether polyol, there is typical polymerization
The superperformance of the high support performance of object polyalcohol, and have lower cost, polymer polyatomic alcohol can be substituted, in foaming
It uses.
To achieve the above objectives, the invention adopts the following technical scheme:
A kind of preparation method of inorganic modified polyether polyol, first with basic polyether polyalcohol and organic acid containing tertiary amine and
Its derivative reacts under the action of catalyst, prepares based polyether polyol containing tertiary amine；Then it will contain tertiary amine groups polyether polyols
Alcohol is reacted with halogenated alkane, prepares quaternary dispersing agent；Finally by inorganic powder material, the preferably nothing after alkaline activation
Machine powder body material is scattered in basic polyether under the effect of quaternary dispersing agent, and inorganic modified polyether polyol is finally made.
The reaction equation for preparing quaternary dispersing agent is as follows:
In the present invention, the molecular weight of the basic polyether polyalcohol is 500-14000, preferably 2000-10000；Hydroxyl official
Energy degree is 1~6, preferably degree of functionality 3-6；In basic polyether polyalcohol, the weight content of ethylene oxide is preferably 2-15wt%.
In the present invention, the structural formula of the organic acid containing tertiary amine and its derivative is as follows:
Wherein:
R is hydrogen atom or 1~4 carbon saturated hydrocarbyl or unsaturated alkyl, preferably hydrogen atom or methyl；
R1And R2It can be the same or different, be C6~C18 aliphatic group or the aryl radical of C6~C18, preferably benzene
Base, methyl, ethyl, butyl, isobutyl group, the octyl of linear chain or branched chain, allyl, more preferably methyl and ethyl.
In the present invention, during preparing tertiary amine based polyether polyol, 50-120 DEG C of reaction temperature, preferably 80-110 DEG C；Instead
1-5h, preferably 2-3h between seasonable.
In the present invention, during preparing tertiary amine based polyether polyol, the catalysts are lewis acid catalyst,
Such as the metatitanic acid tert-butyl ester, p-methyl benzenesulfonic acid, calcium naphthenate, resin cation and various inorganic or organic acid；It can be used alone,
Also it can be selected one such or a variety of.As a kind of implementable solution, p-methyl benzenesulfonic acid or the metatitanic acid tert-butyl ester can be selected.
In the present invention, the quaternary amine based polyether polyol of preparation is used directly for the next step, after can also being handled again
It is reacted, common processing mode such as distills, rectifying, absorption, extraction means.It is preferred that being directly used in without processing next
The reaction of step.
In the present invention, during preparing quaternary amine based polyether polyol, the dosage of basic polyether polyalcohol with containing tertiary amine it is organic
Acid and its derivative molar ratio 2:1-1:2, preferably 0.9~1.1:1, catalyst amount is the 0.1wt%- of basic polyethers dosage
5wt%, preferably 0.1wt%-2wt%.
In the present invention, the saturation of preferably 1~18 carbon of alkyl halide or the aromatic hydrocarbon of unsaturated aliphatic hydrocarbon or 6~18 carbon
Chloro or bromo or iodo compound, the bromo or iodo compound of the saturated alkane class of preferably 1~4 carbon, more preferable iodine
Methane or bromoethane.
Alkyl halide dosage is molar ratio 2:1-1:2 with organic acid containing tertiary amine and its derivative in the present invention, preferably 0.8~
1.2:1。
In the present invention, the reaction temperature that based polyether polyol containing tertiary amine is reacted with halogenated alkane is 80-150 DEG C, excellent
Select 100-130 DEG C；Reaction time 0.5-5h, preferably 1-2h.
In the present invention, during preparing inorganic modified polyether polyol, reaction kettle whipped form is single paddles of page two, single to promote
Paddle, table roller turbine, double propulsion paddles, double-arc spline turbine promote paddle on lower disc turbine, wherein to guarantee good mass transfer effect
Fruit preferably promotes paddle on lower disc turbine.
In the present invention, during preparing inorganic modified polyether polyol, with inorganic powder material and basic polyether polyalcohol
Total amount meter, inorganic powder material additional amount 10-80wt%, preferably 20-5wt0%；Basic polyether polyalcohol dosage 20-90wt%,
It is preferred that 50-80wt%；Amine salt type polyether polyol (dispersing agent) additional amount is the 10wt%-40wt% of basic polyethers amount, preferably
20wt%-30wt%.
In the present invention, it is by titanium dioxide that inorganic powder material, which is the alkaline silicon dioxide or alkaline titanium dioxide after activation,
Silicon or titanium dioxide are handled in alkaline medium to be obtained, wherein it is preferred that alkaline silicon dioxide；Such as it can be Wacker Chemical Co., Ltd
'sH15.Inorganic powder material partial size 100-1000nm, preferably 200-500nm.
In the present invention, during preparing inorganic modified polyether polyol, 30-140 DEG C of reaction temperature, preferably 80-120 DEG C；
Quaternary amine salt form dispersing agent is preferentially added into basic polyether, stirs 0.5-2h, preferably 1-1.5h；Inorganic powder material is added,
Time 1-6h, preferably 2-4h is added in inorganic powder material.
It is polynary using inorganic process modified polyether to solve the problems, such as smell existing for modified polyether polylol in the present invention
Alcohol, to prepare the mineral-modified polyether polyol of high solids content (47-48wt%), from the above mentioned, polymer polyatomic alcohol product
Existing smell mostlys come from initiator azo-compound and its decomposes production object ester type compound.Inorganic modified polyether polyols
Initiation reaction is not present in alcohol, while smell problem is also not present in the inorganic substances being added, experiments have shown that can effectively mitigate made
The smell problem of standby polyether polyol.
In the present invention, the means for promoting inorganic modified polyether polyol are to be consolidated small particle with a kind of novel stabilizer
State oxide is stably dispersed in polyether polyol, so that prepared inorganic modified polyether polyol has preferable stablize
Property, since finished product inorganic powder cost advantage is obvious, additionally it is possible to be effectively reduced cost.
The polyether polyol prepared by inorganic modified method, reaction process is simple, and temperature and pressure control require low, life
It produces at low cost；Any penetrating odor is not present since there is no the use of monomer；And due to depositing for self-control two-phase dispersing agent
Prepared polyether polyol is with good stability, is not in lamination after standing 200h.
Specific embodiment
Further description is now done to the present invention by following embodiment, but the present invention is not limited to this.
Raw material
The part material used in following embodiment or comparative example is illustrated below:
It is to purchase from the chemical pure of Aladdin reagent in the case that involved all materials are not specified in embodiment
Reagent.
Test instrument
Residual single analysis is analyzed using GC-MS: gas phase instrument model: Agilent 7890-5975C insert XL-MSD
with Triple-Axis Detector；Chromatographic column: DB-5MS (30m × 0.25mm × 0.25 μm)；MS parameter: vacuum pump: whirlpool
Wheel pump, ion source: EI, scanning mode: SIM, ion source temperature: 250 DEG C.Viscosity measurement: using Brookfield DV- II+
Pro viscosity meter, rotor used by same RV6.Measuring shear viscosity torque is 50.
Embodiment 1
Prepare quaternary amine based polyether polyol: basis is added into reaction kettle using paddle is promoted on lower disc turbine for reaction kettle
PolyethersF3135 (ten thousand magnificent chemical productions, functional group's degree 3, hydroxyl value 35, weight average molecular weight 5000, ethylene oxide content
14%) it is poly- that basis is added in dosage and N, the reactant of N- dimethylamino methyl acetate (Aladdin reagent) molar ratio 0.95:1
The Catalyzed by p-Toluenesulfonic Acid agent of the dosage 0.5wt% of ethoxylated polyhydric alcohol, 90 DEG C of reaction temperature, constantly with diaphragm pump to body during reaction
System carries out the water abjection of reaction generation, reaction time 2h.After first step reaction, it is directly added into and basic polyether polyalcohol 1.05:1
The bromoethane of molar ratio, 100 DEG C of reaction 2h obtain quaternary amine salt form dispersing agent.
Prepare inorganic modified polyether polyol: reaction kettle equally uses and promotes paddle on lower disc turbine, will be added in kettle
80 DEG C of reaction temperature, 300g silicon-dioxide powdery material is added in 100g dispersing agent, 600g basic polyether polyalcohol under agitation
Material is added time 2h, persistently stirs 2h after the completion of charging, reaction terminates.
Embodiment 2
Prepare quaternary amine based polyether polyol: reaction kettle is added using paddle is promoted on lower disc turbine into reaction kettleBasic polyether is added in the dosage and N of F3135, the reactant of N- dimethylamino ethyl acetate molar ratio 0.95:1
The Catalyzed by p-Toluenesulfonic Acid agent of the dosage 0.5wt% of polyalcohol, 100 DEG C of reaction temperature, constantly with diaphragm pump to body during reaction
System carries out the water abjection of reaction generation, reaction time 2h.After first step reaction, it is directly added into and basic polyether polyalcohol 1.05:1
The bromoethane of molar ratio, 100 DEG C of reaction 1h obtain quaternary amine salt form dispersing agent.
Prepare inorganic modified polyether polyol: reaction kettle equally uses and promotes paddle on lower disc turbine, will be added in kettle
80 DEG C of reaction temperature, 400g silicon-dioxide powdery material is added in 100g dispersing agent, 500g basic polyether polyalcohol under agitation
Material is added time 2h, persistently stirs 2h after the completion of charging, reaction terminates.
Embodiment 3
Prepare quaternary amine based polyether polyol: reaction kettle is added using paddle is promoted on lower disc turbine into reaction kettleBasic polyether is added in the dosage and N of F3135, the reactant of N- dimethylamino ethyl acetate molar ratio 0.95:1
The Catalyzed by p-Toluenesulfonic Acid agent of the dosage 0.5wt% of polyalcohol, 110 DEG C of reaction temperature, constantly with diaphragm pump to body during reaction
System carries out the water abjection of reaction generation, reaction time 2h.After first step reaction, it is directly added into and basic polyether polyalcohol 1.05:1
The bromoethane of molar ratio, 100 DEG C of reaction 1.5h obtain quaternary amine salt form dispersing agent.
Prepare inorganic modified polyether polyol: reaction kettle equally uses and promotes paddle on lower disc turbine, will be added in kettle
80 DEG C of reaction temperature, 500g silicon-dioxide powdery material is added in 100g dispersing agent, 400g basic polyether polyalcohol under agitation
Material is added time 2h, persistently stirs 2h after the completion of charging, reaction terminates.
Embodiment 4
Prepare quaternary amine based polyether polyol: reaction kettle is added using paddle is promoted on lower disc turbine into reaction kettleIt is polynary that basic polyether is added in the dosage and N of F3135, the reactant of N- dimethylamino methyl acetate molar ratio 1:1
The Catalyzed by p-Toluenesulfonic Acid agent of the dosage 1wt% of alcohol, constantly carries out system with diaphragm pump during reaction anti-by 90 DEG C of reaction temperature
The water abjection that should be generated, reaction time 2h.After first step reaction, it is directly added into and basic polyether polyalcohol 1.03:1 molar ratio
Iodomethane, 110 DEG C of reaction 2h obtain quaternary amine salt form dispersing agent.
Prepare inorganic modified polyether polyol: reaction kettle equally uses and promotes paddle on lower disc turbine, will be added in kettle
80 DEG C of reaction temperature, 300g silicon-dioxide powdery material is added in 130g dispersing agent, 570g basic polyether polyalcohol under agitation
Material is added time 2h, persistently stirs 2h after the completion of charging, reaction terminates.
Embodiment 5
Prepare quaternary amine based polyether polyol: reaction kettle is added using paddle is promoted on lower disc turbine into reaction kettleIt is polynary that basic polyether is added in the dosage and N of F3135, the reactant of N- dimethylamino ethyl acetate molar ratio 1:1
The Catalyzed by p-Toluenesulfonic Acid agent of the dosage 1wt% of alcohol, constantly carries out system with diaphragm pump during reaction by 100 DEG C of reaction temperature
The water abjection that reaction generates, reaction time 2h.After first step reaction, it is directly added into and basic polyether polyalcohol 1.03:1 molar ratio
Iodomethane, 110 DEG C of reaction 1h obtain quaternary amine salt form dispersing agent.
Prepare inorganic modified polyether polyol: reaction kettle equally uses and promotes paddle on lower disc turbine, will be added in kettle
80 DEG C of reaction temperature, 400g silicon-dioxide powdery material is added in 130g dispersing agent, 470g basic polyether polyalcohol under agitation
Material is added time 2h, persistently stirs 2h after the completion of charging, reaction terminates.
Embodiment 6
Prepare quaternary amine based polyether polyol: reaction kettle is added using paddle is promoted on lower disc turbine into reaction kettleIt is polynary that basic polyether is added in the dosage and N of F3135, the reactant of N- dimethylamino methyl acetate molar ratio 1:1
The Catalyzed by p-Toluenesulfonic Acid agent of the dosage 1wt% of alcohol, constantly carries out system with diaphragm pump during reaction by 110 DEG C of reaction temperature
The water abjection that reaction generates, reaction time 2h.After first step reaction, it is directly added into and basic polyether polyalcohol 1.03:1 molar ratio
Iodomethane, 110 DEG C of reaction 1.5h obtain quaternary amine salt form dispersing agent.
Prepare inorganic modified polyether polyol: reaction kettle equally uses and promotes paddle on lower disc turbine, will be added in kettle
80 DEG C of reaction temperature, 500g silicon-dioxide powdery material is added in 130g dispersing agent, 370g basic polyether polyalcohol under agitation
Material is added time 2h, persistently stirs 2h after the completion of charging, reaction terminates.
Embodiment 7
Prepare quaternary amine based polyether polyol: reaction kettle is added using paddle is promoted on lower disc turbine into reaction kettleBasic polyether is added in the dosage and N of F3135, the reactant of N- dimethylamino methyl acetate molar ratio 1.05:1
The Catalyzed by p-Toluenesulfonic Acid agent of the dosage 2wt% of polyalcohol, 90 DEG C of reaction temperature, during reaction constantly with diaphragm pump to system into
The water abjection that row reaction generates, reaction time 2h.After first step reaction, it is directly added into and 1.05:1 moles of basic polyether polyalcohol
The iodomethane of ratio, 120 DEG C of reaction 2h obtain quaternary amine salt form dispersing agent.
Prepare inorganic modified polyether polyol: reaction kettle equally uses and promotes paddle on lower disc turbine, will be added in kettle
80 DEG C of reaction temperature, 300g silicon-dioxide powdery material is added in 150g dispersing agent, 550g basic polyether polyalcohol under agitation
Material is added time 2h, persistently stirs 2h after the completion of charging, reaction terminates.
Embodiment 8
Prepare quaternary amine based polyether polyol: reaction kettle is added using paddle is promoted on lower disc turbine into reaction kettleBasic polyether is added in the dosage and N of F3135, the reactant of TMSDMA N dimethylamine ethyl molar ratio 1.05:1
The Catalyzed by p-Toluenesulfonic Acid agent of the dosage 2wt% of polyalcohol, 100 DEG C of reaction temperature, constantly with diaphragm pump to system during reaction
Carry out the water abjection of reaction generation, reaction time 2h.After first step reaction, it is directly added into and rubs with basic polyether polyalcohol 1.05:1
The iodomethane of your ratio, 120 DEG C of reaction 1.5h obtain quaternary amine salt form dispersing agent.
Prepare inorganic modified polyether polyol: reaction kettle equally uses and promotes paddle on lower disc turbine, will be added in kettle
80 DEG C of reaction temperature, 400g silicon-dioxide powdery is added in 150g dispersing agent, 4500g basic polyether polyalcohol under agitation
Material is added time 2h, persistently stirs 2h after the completion of charging, reaction terminates.
Embodiment 9
Prepare quaternary amine based polyether polyol: reaction kettle is added using paddle is promoted on lower disc turbine into reaction kettleBasic polyether is added in the dosage and N of F3135, the reactant of N- dimethylamino methyl acetate molar ratio 1.05:1
The Catalyzed by p-Toluenesulfonic Acid agent of the dosage 2wt% of polyalcohol, 110 DEG C of reaction temperature, constantly with diaphragm pump to system during reaction
Carry out the water abjection of reaction generation, reaction time 2h.After first step reaction, it is directly added into and rubs with basic polyether polyalcohol 1.05:1
The iodomethane of your ratio, 100 DEG C of reaction 1h obtain quaternary amine salt form dispersing agent.
Prepare inorganic modified polyether polyol: reaction kettle equally uses and promotes paddle on lower disc turbine, will be added in kettle
80 DEG C of reaction temperature, 500g silicon-dioxide powdery material is added in 150g dispersing agent, 350g basic polyether polyalcohol under agitation
Material is added time 2h, persistently stirs 2h after the completion of charging, reaction terminates.
| Case study on implementation | Admittedly containing % | Viscosity | 200h stability |
| 1 | 29.3 | 2489 | √ |
| 2 | 39.1 | 5691 | √ |
| 3 | 47.8 | 6437 | √ |
| 4 | 28.9 | 2786 | √ |
| 5 | 38.7 | 5781 | √ |
| 6 | 47.2 | 6760 | √ |
| 7 | 28.3 | 2911 | √ |
| 8 | 37.5 | 5773 | √ |
| 9 | 47.4 | 6954 | √ |
| Comparative example | 44 | 5000 or so |
With it is commercially availablePOP2045 (ten thousand magnificent chemical productions) is compared, and viscosity is slightly higher, and stability is preferable, but cost
Low, odorlessness has stronger advantage." √ " is indicated: standing 200h is not stratified or settles.
Claims (10)
1. a kind of preparation method of inorganic modified polyether polyol comprising the steps of: first with basic polyether polyalcohol with contain
Tertiary amine organic acid and its derivative react under the action of catalyst, prepare based polyether polyol containing tertiary amine；Then it will contain uncle
Amido polyether polyol is reacted with halogenated alkane, prepares quaternary dispersing agent；Finally by inorganic powder material, in quaternary ammonium
It is scattered in basic polyether under the effect of salt form dispersing agent, inorganic modified polyether polyol is finally made.
2. preparation method as described in claim 1, which is characterized in that the basic polyether polyol molecular weight is 500-
14000, preferably 2000-10000；Hydroxy functionality is 1~6, preferably degree of functionality 3-6；In basic polyether polyalcohol, ethylene oxide
Weight content be preferably 2-15wt%.
3. preparation method as claimed in claim 1 or 2, which is characterized in that the organic acid containing tertiary amine and its derivative
Structural formula is as follows:
Wherein:
R is hydrogen atom or 1~4 carbon saturated hydrocarbyl or unsaturated alkyl, preferably hydrogen atom or methyl；
R1It is identical or different with R2, it is 1~18 carbon saturated hydrocarbyl or aryl radical, preferred phenyl, methyl, ethyl, butyl, different
Butyl, the octyl of linear chain or branched chain, allyl, more preferably methyl and ethyl；And/or basic polyether polyalcohol with contain tertiary amine
Organic acid and its derivative molar ratio 2:1-1:2, preferably 0.9~1.1:1.
4. preparation method as claimed in any one of claims 1-3, which is characterized in that basic polyether polyalcohol has with containing tertiary amine
The reaction condition of machine acid and its derivative are as follows: 50-120 DEG C of reaction temperature, preferably 80-110 DEG C；Reaction time 1-5h, preferably 2-
3h。
5. such as preparation method of any of claims 1-4, which is characterized in that described to prepare tertiary amine based polyether polyol
Process, catalysts are lewis acid catalyst, such as the metatitanic acid tert-butyl ester, p-methyl benzenesulfonic acid, calcium naphthenate, resin cation
One of or it is a variety of；It is preferred that p-methyl benzenesulfonic acid and/or the metatitanic acid tert-butyl ester；And/or catalyst amount is basic polyethers dosage
0.1wt%-5wt%, preferably 0.5wt%-2wt%.
6. preparation method according to any one of claims 1 to 5, which is characterized in that described prepares quaternary dispersing agent
In the process, the alkyl halide is the saturation of 1~18 carbon or the chloro or bromo or iodo compound of insatiable hunger and/or aromatic hydrocarbon, excellent
Select the bromo or iodo compound of the saturated alkane class of 1~4 carbon, more preferable iodomethane and/or bromoethane；And/or alkyl halide
Dosage is the molar ratio 2:1-1:2, preferably 0.8~1.2:1 with organic acid containing tertiary amine and its derivative；
And/or the reaction temperature that based polyether polyol containing tertiary amine is reacted with halogenated alkane is 80-150 DEG C, preferably 100-
130℃；Reaction time 0.5-5h, preferably 1-2h.
7. such as preparation method of any of claims 1-6, which is characterized in that prepare inorganic modified polyether polyol mistake
Cheng Zhong, reaction kettle whipped form is single paddles of page two, single to promote paddle, table roller turbine, double propulsion paddles, double-arc spline turbine, lower disc
Paddle is promoted on turbine, preferably promotes paddle on lower disc turbine.
8. preparation method as claimed in claim 7, which is characterized in that with inorganic powder material and basic polyether polyalcohol total amount
Meter, inorganic powder material additional amount 10-80wt%, preferably 20-50wt%；Basic polyether polyalcohol dosage 20-90wt%, preferably
50-80wt%；Quaternary amine salt form dispersing agent additional amount is the 10wt%-40wt%, preferably 20wt%-30wt% of basic polyethers amount.
9. preparation method as claimed in claim 8, which is characterized in that inorganic powder material is alkaline silicon dioxide or alkalinity two
Titanium oxide, wherein it is preferred that alkaline silicon dioxide；Powder body material partial size 100-1000nm, preferably 200-500nm.
10. preparation method of any of claims 1-9, which is characterized in that prepare inorganic modified polyether polyol
Reaction temperature is 30-140 DEG C, preferably 80-120 DEG C；Time 1-6h, preferably 2-4h is added in powder body material；Preferentially to basic polyether
Middle addition quaternary amine salt form dispersing agent stirs 0.5-2h, preferably 1-1.5h；Inorganic powder material is added, inorganic powder material adds
Angle of incidence 1-6h, preferably 2-4h.
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|---|---|---|---|---|
| CN111116888A (en) * | 2019-12-20 | 2020-05-08 | 万华化学集团股份有限公司 | Quaternary ammonium salt type dispersing agent and preparation method thereof, and preparation method of inorganic modified polyether polyol |
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| CN111116888B (en) * | 2019-12-20 | 2022-09-20 | 万华化学集团股份有限公司 | Quaternary ammonium salt type dispersing agent and preparation method thereof, and preparation method of inorganic modified polyether polyol |
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| CN113956462B (en) * | 2021-10-21 | 2023-07-14 | 万华化学集团股份有限公司 | Preparation method of polyether polyol with low aldehyde content |
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