CN106496543A - A kind of preparation method of allyl alcohol polyether glycidyl ether - Google Patents
A kind of preparation method of allyl alcohol polyether glycidyl ether Download PDFInfo
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- CN106496543A CN106496543A CN201610941343.7A CN201610941343A CN106496543A CN 106496543 A CN106496543 A CN 106496543A CN 201610941343 A CN201610941343 A CN 201610941343A CN 106496543 A CN106496543 A CN 106496543A
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- Prior art keywords
- allyl alcohol
- glycidyl ether
- alcohol polyether
- preparation
- reaction
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- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 229920000570 polyether Polymers 0.000 title claims abstract description 56
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 51
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 239000002994 raw material Substances 0.000 claims abstract description 34
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000007921 spray Substances 0.000 claims abstract description 30
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 18
- 238000005507 spraying Methods 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006073 displacement reaction Methods 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 20
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
- 238000005516 engineering process Methods 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 2
- 238000005292 vacuum distillation Methods 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 238000000746 purification Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 9
- 238000007086 side reaction Methods 0.000 abstract description 8
- 230000004913 activation Effects 0.000 abstract description 2
- 230000001629 suppression Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000002118 epoxides Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 208000035126 Facies Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 1
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- VIRPUNZTLGQDDV-UHFFFAOYSA-N chloro propanoate Chemical compound CCC(=O)OCl VIRPUNZTLGQDDV-UHFFFAOYSA-N 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000675 fabric finishing Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000009962 finishing (textile) Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- RBNPOMFGQQGHHO-UHFFFAOYSA-N glyceric acid Chemical compound OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- -1 sodium alkoxide Chemical class 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/27—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms
- C07D301/28—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms by reaction with hydroxyl radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
- C07D303/24—Ethers with hydroxy compounds containing no oxirane rings with polyhydroxy compounds
- C07D303/27—Ethers with hydroxy compounds containing no oxirane rings with polyhydroxy compounds having all hydroxyl radicals etherified with oxirane containing compounds
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of preparation method of allyl alcohol polyether glycidyl ether, is included in outer circulation spray type reactor, allyl alcohol polyethenoxy ether raw material is added, except oxygen and filling nitrogen displacement protection, opening outer circulation pump carries out high-speed circulating spraying；Control temperature at 10 55 DEG C enters epoxychloropropane raw material and the spraying of liquid caustic soda raw material in reactor, and that realizes three is sufficiently mixed the steps such as reaction, and as body series belong to dynamics Controlling system, and side reaction has been got back enough suppression.Further according to side reaction activation energy high the characteristics of, present invention employs low temperature process carries out kinetic reaction control so that the selectivity of reaction system is higher.The product allyl alcohol polyether glycidyl ether product color for finally giving is less than 40, and ending ratio is more than 96%.
Description
Technical field
The present invention relates to chemical technology field, specifically, is a kind of preparation method of allyl alcohol polyether glycidyl ether.
Background technology
Alkyl capped polyether is led in synthetic lubricant fluid, daily-use chemical industry and preparation medium as the polyethers of unique construction and performance
Domain is widely applied.In strand hydroxyl all by alkyl-substituted alkyl capped polyether and strand containing hydroxyl
Polyethers is compared, with higher chemical stability.Using the good thermostability of alkyl capped polyether, can be used as the non-of function admirable
Ionic surface active agent is used in the oil preparation of chemical fiber high-speed spinning silk, also can be used for resistant to elevated temperatures lubricating oil or heat conduction as additive
In oil.Using its stability to highly basic, can be used in alkaline detergent compositions.In addition, most of alkyl capped polyethers
Also there is suds and low foaming characteristic, therefore be often used as the monomer of defoamer or low-foaming detergent.Multiple manufacture alkane are had before this
The method of base end capped polyether, Williamson (Williamson) method wherein with alkyl halide as alkylating reagent is because of its reactivity
High and obtain the concern of researcher.Known Williamson (Williamson) method such as Japanese Patent Publication speciallys permit clear 48-
22198th, specially permit clear 54-32598 and specially permit in clear 51-203500 and disclose, be with Feldalat NM, metallic sodium, sodium hydroxide or hydrogen-oxygen
The aqueous solution or alcoholic solution for changing potassium makees alkali metal reagent.Above synthetic method is too strong due to reaction system neutral and alkali, therefore closes
Low into the alkyl capped polyether ending ratio for obtaining, product color depth, by-product are more.
Patent US 5,847,229 is proposed, using two-step method, i.e., first by solid sodium hydroxide or potassium hydroxide with contain hydroxyl
The polyethers of base fully reacts the corresponding alkoxide of generation, and then alkoxide is reacted with dimethyl sulfate, can than conventional method compared with
The yield of end capped polyether is significantly increased.But, due to the presence of side reaction, including patent US 5,847,229 interior
There is method, raw material (such as the dimethyl sulfate) usage amount for blocking is more than the 200% of theoretical amount, and closed-end efficiency can be only achieved
More than 90%.
Allyl alcohol polyether glycidyl ether is a kind of epoxide containing soft segment.As intramolecular contains simultaneously
The unsaturated double-bond and epoxide group of activity, with good reactivity and activity.The polyether segment for containing, with low viscous
Degree, flexible the features such as.Thus, allyl alcohol polyether glycidyl ether be widely used in epoxy active diluent, cross-linking agent and
The aspects such as chain-transferring agent, chloride stabilizing agent, fabric finishing agent, modified silicon oil, are a kind of multiduty fine chemical products.
General all based on synthesis short chain class glycidyl ether in existing patent, such as Japan Patent Jpn.KokkyoKoho
07133269 method for disclosing the synthesis of allyl glycidyl ether under sodium hydroxide effect with 1-propenol-3 and epoxychloropropane；
Chinese patent CN1927851A is disclosed with 1-propenol-3 and epoxychloropropane as raw material, in the catalysis open loop sodium hydroxide closed loop of acid
The lower synthesis of allyl glycidyl ether of effect；Chinese patent CN1927852A is disclosed with butanol and epoxychloropropane as raw material,
Synthesize butyl glycidyl ether under the catalysis open loop sodium hydroxide ring closure of acid.And synthesis long-chain in the patent that is reported
Glycidyl ether does not almost have, at the same also there are problems that above-mentioned be susceptible to epoxide group open loop addition generation,
Cause that intermediate by-products are more, the final yield for affecting product.
Chinese patent CN104387576A, CN101928389A, CN102050943A and CN102060989A report contracting
Several preparation methoies of water glycerol ether blocked allyl alcohol polyether, employ allyl alcohol polyether as raw material, by catalyst
NaH, or raw material NaH, or solid base is used as raw material, has prepared glycidyl ether blocked allyl alcohol polyether, but
Exist that cost of material is high to be difficult to promote, the too strong product color depth of raw material alkalescence, the shortcomings of by-product is more.
Content of the invention
The present invention is exactly for various weak points present in prior art, there is provided a kind of allyl alcohol polyether shrinks sweet
The preparation method of oily ether.
The present invention is realized by such technical scheme for reaching above-mentioned purpose：
The invention discloses a kind of preparation method of allyl alcohol polyether glycidyl ether, comprises the following steps：
1) in outer circulation spray type reactor, allyl alcohol polyethenoxy ether raw material is added, except oxygen and filling nitrogen displacement protection, is opened
Opening outer circulation pump carries out high-speed circulating spraying；
2) control temperature at 10-55 DEG C enters epoxychloropropane raw material and the spraying of liquid caustic soda raw material in reactor, realizes
Three is sufficiently mixed reaction, and charging spray time is 3-24 hours, after charging terminates, continues soak cycles spray reaction 3-
After 24 hours, reaction terminates；
3), after reaction terminates, with the aftertreatment technology that with after, filters after distillation under reduced pressure in phosphoric acid, 1-propenol-3 is prepared
Polyethers glycidyl ether.
As further improving, the Sauter mean diameter in outer circulation spray type reactor of the present invention
(SMD, Sauter MeanDiameter) is in 10 300 μ ms.
As further improving, allyl alcohol polyethenoxy ether raw material of the present invention, molecular weight is 150-6000.
As further improving, allyl alcohol polyethenoxy ether of the present invention, the mol ratio of epoxychloropropane and alkali
Example 1:1.01-1.50:1.01-1.50.
As further improving, allyl alcohol polyethenoxy ether of the present invention, the mol ratio of epoxychloropropane and alkali
Example is 1:1.01-1.50:1.01-1.50.
Used as further improving, liquid caustic soda of the present invention is sodium hydrate aqueous solution or potassium hydroxide aqueous solution,
Its mass concentration is 10-50%.
Used as further improving, reaction temperature of the present invention is preferably 15-45 DEG C.
Used as further improving, obtained allyl alcohol polyether glycidyl ether of the present invention is also performed to product essence
System, the first low-boiling point material in vacuum distillation removing system, are then filtrated to get refined allyl alcohol polyether shrink sweet
Oily ether product.
Used as further improving, allyl alcohol polyether glycidyl ether product color of the present invention is blocked less than 40
Rate is more than 96%.
Used as further improving, phosphoric acid of the present invention is 50% phosphoric acid.
Beneficial effects of the present invention are as follows：
1st, the outer circulation spray type reactor of uniqueness is present invention employs, traditional stirred-tank reactor is instead of.Root
According to test, the mass transfer rate of outer circulation spray type reactor improves one than the mass transfer rate of traditional stirred-tank reactor
More than the order of magnitude, the mass transfer between each reaction species in reactor is greatly facilitated, so that reaction may be at power
Learn control.Due to the use of novel external circulation spray type reactor, without the need for adopting phase transfer catalyst in this reaction system.Reaction
Sufficient mass transfer and reaction can be realized in system between organic faciess and liquid caustic soda phase, significant increase reaction efficiency reduces pair
The generation of reaction.The droplet particle diameter of spraying is minimum, so as to have great specific surface area, can be with the epoxy chloropropionate in gas phase
Alkane is contacted rapidly, and is absorbed into rapidly droplet, so as to greatly facilitate the biography in reaction system between each reaction species
Matter process, and the homogeneity of each droplet content concentration is ensure that, have than uniform concentration distribution in stirred tank and greatly carry
Rise, This further reduces the occurrence probability of side reaction, improve selectivity and the efficiency of reaction.
2nd, two kinds of raw materials of liquid caustic soda and epoxychloropropane in the reaction, are continuously added reactor using spray pattern by the present invention
In react with allyl alcohol polyether.On the one hand, in traditional tank reactor, the sodium alkoxide, potassium alcoholate or sodium hydroxide, the hydrogen that use
Potassium oxide be all disposable add, not only alkaline too strong, also so that in system alkali excessive concentration so that reaction system is easily sent out
The a large amount of side reactions of life, cause product color depth, reaction raw materials epoxychloropropane to be consumed in a large number.Therefore adopt core material liquid
Two kinds of raw materials of alkali and epoxychloropropane are continuously added in reactor using spray pattern and are reacted with allyl alcohol polyether, are not only had
Effect reduces the alkalescence of system, also reduces alkali concn in system, so as to effectively evade the generation of side reaction, additionally to anti-
System is answered to carry out, except oxygen and filling nitrogen displacement protection, further ensure that the color and luster of product is excellent.
3rd, as body series belong to dynamics Controlling system, enough suppression and side reaction has been got back.Further basis
The characteristics of side reaction activation energy is high, present invention employs low temperature process carries out kinetic reaction control so that the selection of reaction system
Property is higher.The product allyl alcohol polyether glycidyl ether product color for finally giving is less than 40, and ending ratio is more than 96%.
Product color adopts platinum-cobalt colorimetric method for determining.Product ending ratio is the (reality of product allyl alcohol polyether glycidyl ether
Survey epoxide number/theoretical epoxy value) * 100%.
Description of the drawings
Structural representations of the Fig. 1 for outer circulation spray type reactor.
Specific embodiment
The invention discloses a kind of preparation method of allyl alcohol polyether glycidyl ether, the present invention is with reference to being embodied as
Example makees detailed description further to technical scheme, but the scope of the present invention is not limited to embodiment.
Embodiment 1
(1) in outer circulation spray type reactor (Sauter mean diameter is 10 μm), allyl alcohol polyethenoxy is added
Ether raw material (molecular weight is 150) 150kg, except oxygen and filling nitrogen displacement protection, opening outer circulation pump carries out high-speed circulating spraying.
(2) control temperature is at 10 DEG C, former by epoxychloropropane raw material 93.5kg and liquid caustic soda (10%NaOH solution) 404kg
Material spraying is entered in reactor, realizes the reaction that is sufficiently mixed of three, and charging spray time is 24 hours.After charging terminates,
Continue soak cycles spray reaction after 24 hours, reaction terminates.
(3), after reaction terminates, with the aftertreatment technology that with after, filters after distillation under reduced pressure in 50% phosphoric acid, it is prepared into
Arrive allyl alcohol polyether glycidyl ether.Allyl alcohol polyether glycidyl ether product color is 20, and ending ratio is 96.7%.
Embodiment 2
(1) in outer circulation spray type reactor (Sauter mean diameter is 300 μm), allyl alcohol polyethenoxy is added
Ether raw material (molecular weight is 6000) 600kg, except oxygen and filling nitrogen displacement protection, opening outer circulation pump carries out high-speed circulating spraying.
(2) control temperature is at 55 DEG C, former by epoxychloropropane raw material 13.9kg and liquid caustic soda (50%NaOH solution) 12kg
Material spraying is entered in reactor, realizes the reaction that is sufficiently mixed of three, and charging spray time is 3 hours.After charging terminates, after
After 3 hours, reaction terminates continuous soak cycles spray reaction.
(3), after reaction terminates, with the aftertreatment technology that with after, filters after distillation under reduced pressure in 50% phosphoric acid, it is prepared into
Arrive allyl alcohol polyether glycidyl ether.Allyl alcohol polyether glycidyl ether product color is 22, and ending ratio is 97.7%.
Embodiment 3
(1) in outer circulation spray type reactor (Sauter mean diameter is 50 μm), allyl alcohol polyethenoxy is added
Ether raw material (molecular weight is 500) 500kg, except oxygen and filling nitrogen displacement protection, opening outer circulation pump carries out high-speed circulating spraying.
(2) temperature is controlled at 15 DEG C, by epoxychloropropane raw material 120kg and potassium hydroxide solution (30%KOH solution)
The spraying of 243kg raw materials is entered in reactor, realizes the reaction that is sufficiently mixed of three, and charging spray time is 12 hours.Charging knot
After beam, continue soak cycles spray reaction after 12 hours, reaction terminates.
(3), after reaction terminates, with the aftertreatment technology that with after, filters after distillation under reduced pressure in 50% phosphoric acid, it is prepared into
Arrive allyl alcohol polyether glycidyl ether.Allyl alcohol polyether glycidyl ether product color is 18, and ending ratio is 99.7%.
Embodiment 4
(1) in outer circulation spray type reactor (Sauter mean diameter is 100 μm), allyl alcohol polyethenoxy is added
Ether raw material (molecular weight is 1200) 600kg, except oxygen and filling nitrogen displacement protection, opening outer circulation pump carries out high-speed circulating spraying.
(2) temperature is controlled at 45 DEG C, by epoxychloropropane raw material 56kg and potassium hydroxide solution (33%KOH solution)
The spraying of 103kg raw materials is entered in reactor, realizes the reaction that is sufficiently mixed of three, and charging spray time is 15 hours.Charging knot
After beam, continue soak cycles spray reaction after 10 hours, reaction terminates.
(3), after reaction terminates, with the aftertreatment technology that with after, filters after distillation under reduced pressure in 50% phosphoric acid, it is prepared into
Arrive allyl alcohol polyether glycidyl ether.Allyl alcohol polyether glycidyl ether product color is 20, and ending ratio is 99.8%.
Embodiment 5
(1) in outer circulation spray type reactor (Sauter mean diameter is 50 μm), allyl alcohol polyethenoxy is added
Ether raw material (molecular weight is 800) 400kg, except oxygen and filling nitrogen displacement protection, opening outer circulation pump carries out high-speed circulating spraying.
(2) temperature is controlled at 30 DEG C, by epoxychloropropane raw material 56kg and potassium hydroxide solution (33%KOH solution)
The spraying of 103kg raw materials is entered in reactor, realizes the reaction that is sufficiently mixed of three, and charging spray time is 15 hours.Charging knot
After beam, continue soak cycles spray reaction after 10 hours, reaction terminates.
(3), after reaction terminates, with the aftertreatment technology that with after, filters after distillation under reduced pressure in 50% phosphoric acid, it is prepared into
Arrive allyl alcohol polyether glycidyl ether.Allyl alcohol polyether glycidyl ether product color is 18, and ending ratio is 99.9%.
Finally, in addition it is also necessary to it is noted that listed above is only that the present invention is embodied as example.Obviously, the present invention not
It is limited to above example, there can also be many deformations.One of ordinary skill in the art can be straight from present disclosure
The all deformations that derives or associate are connect, protection scope of the present invention is considered as.
Claims (10)
1. a kind of preparation method of allyl alcohol polyether glycidyl ether, it is characterised in that comprise the following steps：
1) in outer circulation spray type reactor, allyl alcohol polyethenoxy ether raw material is added, except oxygen and filling nitrogen displacement protection, is opened outer
Circulating pump carries out high-speed circulating spraying；
2) control temperature at 10-55 DEG C enters epoxychloropropane raw material and the spraying of liquid caustic soda raw material in reactor, realizes three
Be sufficiently mixed reaction, charging spray time is 3-24 hours, after charging terminates, continues soak cycles spray reaction 3-24 little
Shi Hou, reaction terminate；
3), after reaction terminates, with the aftertreatment technology that with after, filters after distillation under reduced pressure in phosphoric acid, allyl alcohol polyether is prepared
Glycidyl ether.
2. the preparation method of allyl alcohol polyether glycidyl ether according to claim 1, it is characterised in that described outer follow
Sauter mean diameter (SMD, Sauter MeanDiameter) in ring spray type reactor is in 10 300 μ ms.
3. the preparation method of allyl alcohol polyether glycidyl ether according to claim 1 and 2, it is characterised in that described
Allyl alcohol polyethenoxy ether raw material, molecular weight are 150-6000.
4. the preparation method of allyl alcohol polyether glycidyl ether according to claim 1 and 2, it is characterised in that described
The molar ratio 1 of allyl alcohol polyethenoxy ether, epoxychloropropane and alkali:1.01-1.50:1.01-1.50.
5. the preparation method of allyl alcohol polyether glycidyl ether according to claim 3, it is characterised in that described allyl
The molar ratio of polyoxyethylenated alcohol, epoxychloropropane and alkali is 1:1.01-1.50:1.01-1.50.
6. the preparation method of the allyl alcohol polyether glycidyl ether according to claim 1 or 2 or 5, it is characterised in that described
Liquid caustic soda be sodium hydrate aqueous solution or potassium hydroxide aqueous solution, its mass concentration is 10-50%.
7. the preparation method of allyl alcohol polyether glycidyl ether according to claim 6, it is characterised in that the reaction temperature
Degree is preferably 15-45 DEG C.
8. the preparation method of allyl alcohol polyether glycidyl ether according to claim 6, it is characterised in that described is obtained
Allyl alcohol polyether glycidyl ether be also performed to product purification, the low-boiling point material in vacuum distillation removing system first, so
Afterwards through being filtrated to get refined allyl alcohol polyether (+)-2,3-Epoxy-1-propanol ether product.
9. the preparation method of the allyl alcohol polyether glycidyl ether according to claim 1 or 2 or 5 or 7 or 8, its feature exist
In described allyl alcohol polyether glycidyl ether product color is less than 40, and ending ratio is more than 96%.
10. the preparation method of allyl alcohol polyether glycidyl ether according to claim 1, it is characterised in that described phosphorus
Acid is 50% phosphoric acid.
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