CN106832253A - A kind of preparation method of alkyl capped polyether - Google Patents
A kind of preparation method of alkyl capped polyether Download PDFInfo
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- CN106832253A CN106832253A CN201611234751.5A CN201611234751A CN106832253A CN 106832253 A CN106832253 A CN 106832253A CN 201611234751 A CN201611234751 A CN 201611234751A CN 106832253 A CN106832253 A CN 106832253A
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- capped polyether
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- 229920000570 polyether Polymers 0.000 title claims abstract description 76
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 60
- 125000000217 alkyl group Chemical group 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 18
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 17
- 125000005910 alkyl carbonate group Chemical group 0.000 claims abstract description 11
- 239000000376 reactant Substances 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 10
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 8
- 230000003472 neutralizing effect Effects 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 3
- 238000012661 block copolymerization Methods 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical group COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 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 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical group [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 6
- 150000001350 alkyl halides Chemical class 0.000 abstract description 6
- 150000008051 alkyl sulfates Chemical class 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 231100000614 poison Toxicity 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000007096 poisonous effect Effects 0.000 abstract description 2
- 239000012043 crude product Substances 0.000 abstract 1
- 238000006386 neutralization reaction Methods 0.000 abstract 1
- 150000003384 small molecules Chemical class 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000010792 warming Methods 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229920001296 polysiloxane Polymers 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 150000005682 diethyl carbonates Chemical class 0.000 description 2
- 150000005686 dimethyl carbonates Chemical class 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- -1 siloxane structure Chemical group 0.000 description 2
- SYXYWTXQFUUWLP-UHFFFAOYSA-N sodium;butan-1-olate Chemical group [Na+].CCCC[O-] SYXYWTXQFUUWLP-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-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
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 239000000675 fabric finishing Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000009962 finishing (textile) Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
Classifications
-
- 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
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polyethers (AREA)
Abstract
The invention belongs to the synthesis technical field of end capped polyether, it is related to a kind of preparation method of alkyl capped polyether, further belongs to the synthesis technical field of alkyl capped polyether.Polyethers carries out alcohol salinization reaction with alkoxidation reagent, small molecule is removed under the vacuum that pressure is 0.07~0.10Mpa, reaction is added dropwise alkyl carbonate and continues to react after terminating, obtain alkyl capped polyether crude product, then by obtaining alkyl capped polyether after neutralization, filtration treatment.Present invention uses new green end-capping reagent alkyl carbonate, alkyl capped polyether is prepared as the polyether reactant containing hydroxyl in the substitute of the poisonous end-capping reagent such as alkyl sulfate, alkyl halide, with molecule, the features such as with nontoxic, non-environmental-pollution.
Description
Technical field
The invention belongs to the synthesis technical field of end capped polyether, it is related to a kind of preparation method of alkyl capped polyether.
Background technology
Hydroxyl is all by alkyl-substituted alkyl capped polyether compared with the polyethers containing hydroxyl in strand in strand
With chemical stability higher.The special construction of end capped polyether result in its special process based prediction model.Using alkyl
The good heat resistance of end capped polyether, can be used for the finish of chemical fiber high-speed spinning silk as the nonionic surfactant of function admirable
In, can also be used in resistant to elevated temperatures lubricating oil or conduction oil as additive；Using its stability to highly basic, can be used for highly basic
In property detergent compositions；In addition, therefore end capped polyether has extensively in polyurethane foams stabilizers, defoamer and fabric finishing agent is prepared
General purposes.
At present, the end blocking method of polyethers can be divided mainly into etherified sealed end, esterification end-blocking and crosslinking end-blocking.Existing closed-end technology
In, the most frequently used and general method is etherified sealed end.Traditional closed-end technology is in the basic conditions, by polyethers and alkylsurfuric acid
Ester or alkyl halide reaction generation end capped polyether.Such as United States Patent (USP) 4,301,083 describes water-soluble in NaOH or potassium hydroxide
In liquid, polyethers and the alkyl halide reaction of hydroxyl generate alkyl-blocked polyethers；United States Patent (USP) 4,922,029 and Chinese patent
02150754.6 describes in NaOH or potassium hydroxide aqueous solution, polyethers and dimethyl suflfate or the sulfuric acid two of hydroxyl
The method that ethyl ester reaction prepares alkyl capped polyether.Above-mentioned end-capping reagent used is alkyl sulfate, two kinds of Toxics of alkyl halide
Matter, belongs to high-risk, high poison, highly corrosive medicine, and needed to use in building-up process in substantial amounts of alkali and generation acid, generation
Inorganic salts can increase separate and purification difficulty.Chinese patent 201210275167.X is introduced, and under weak basic condition, is utilized
Diethyl carbonate is directly blocked to polyether silicone, and generation polyether segment end is the polyether silicone of ethyl carbonate, and
It is applied in foaming polyurethane material.And the method makes directly to be connect with base catalyst in the reaction in polyether silicone
Touch, siloxane structure can be caused to reset, destroy polyether silicone structure；Because the viscosity of polyether silicone is far above polyether polyols
Alcohol, hinders activity hydroxy and base catalyst, the contact of diethyl carbonate, causes ending ratio generally relatively low；By terminal hydroxyl
Ethylene ester group is converted into, belongs to esterification end-blocking category, ester group facile hydrolysis, stability is poor.
The content of the invention
The present invention provides a kind of preparation method of alkyl capped polyether, and its technical problem to be solved uses new
Green Chemistry reagent alkyl carbonate, as containing in the substitute of the poisonous end-capping reagent such as alkyl sulfate, alkyl halide, with molecule
The polyether reactant of hydroxyl prepares alkyl capped polyether, the features such as this method has nontoxic, non-environmental-pollution.Prepared by the present invention
Alkyl capped polyether Stability Analysis of Structures, can prepare polyether silicone with the organosiloxane reaction containing Si-H functional groups.
The present invention is achieved through the following technical solutions the purpose of the present invention, alkyl-blocked poly- the invention provides one kind
The preparation method of ether：
With alkyl carbonate as end-capping reagent, the polyethers containing hydroxyl prepares alkyl capped polyether as raw material with strand；
Polyether segment is homopolymerization, random copolymerization or block copolymerization in the polyethers containing hydroxyl；
The polyether structure formula containing hydroxyl is shown in (I) formula：
A[(OCH2-CHR1)x-OH]y (I)
Wherein：A is the chain radicals of C1-C20, R1It is-H, methyl or ethyl, the natural number of x=2-250, y=1's-10
Natural number；
The alkyl capped polyether general structure is shown in (II) formula：
A[(OCH2-CHR1)x-OR2]y (II)
Wherein R2It is methyl, ethyl or phenyl；
The preparation method of the alkyl capped polyether is comprised the following steps
1) at ambient temperature, will be permanent in the polyethers containing hydroxyl of above-mentioned (I) formula and alkoxidation reagent addition reactor
Temperature reaction, while vacuum removal micromolecular compound；
2) to step 1) middle addition alkyl carbonate continuation reaction；
3) reactant obtains polyethers (II), i.e. alkyl capped polyether by after neutralizing, filtering removal solid matter.
Preferably, step 1) in 25~120 DEG C of reaction temperature, it is 0.2~5 hour reaction time, described poly- containing hydroxyl
Ether is 1 with the molar ratio of alkoxidation reagent:1.0~3.0.
Preferably, step 1) described in alkoxidation reagent be in NaOH, potassium hydroxide, sodium methoxide or potassium methoxide
Plant or various, or NaOH, potassium hydroxide aqueous solution and sodium methoxide, potassium methoxide alcoholic solution；
Preferably, step 2) alkyl carbonate be dimethyl carbonate, diethyl carbonate or diphenyl carbonate.
Preferably, step 2) in 100~150 DEG C of reaction temperature, 0.2~5 hour reaction time, wherein poly- containing hydroxyl
Ether (I) is 1 with the molar ratio of alkyl carbonate:1.0~5.0.
Preferably, step 1) in vacuum removal micromolecular compound vacuum pressure be -0.07~-0.10Mpa, during removing
Between be 1~3h.
Compared with prior art, the beneficial effects of the invention are as follows：
It is of the invention it is critical that used new Green Chemistry reagent alkyl carbonate as end-capping reagent, substitute
The conventional toxic end-capping reagents such as alkyl sulfate, alkyl halide, the characteristics of with nontoxic, non-environmental-pollution, and product is easily located
Reason, is capable of achieving Green Chemistry end-blocking route.
Specific embodiment
To make the object, technical solutions and advantages of the present invention of greater clarity, with reference to specific embodiment, to this
Invention is further described.It should be understood that these descriptions are merely illustrative, and it is not intended to limit the scope of the present invention.
Closed-end efficiency of the present invention is calculated as follows formula and calculates gained：
The hydroxyl value of polyethers and end capped polyether in embodiment, according to the world《Plastics PPG third portion：Hydroxyl value
Determine》(GB-T12008.3-2009) standard test, its ending ratio is measured to alkyl capped polyether prepared by embodiment.
Embodiment 1
In the 2L reactors equipped with agitator, allyl alcohol polyether (EO/PO=35/55, random) 1000g is added, added
NaOH 85g, is warming up to 110~120 DEG C and reacts 2 hours, and keep simultaneously pressure in autoclave it is constant -0.08~-
0.10Mpa, vacuum removal micromolecular compound.Reaction is cooled to 40~45 DEG C after terminating, and is slowly added dropwise 285g dimethyl carbonates
Afterwards, 130~140 DEG C are warming up to react 3 hours.After end, 50 DEG C are cooled to, then after neutralizing, being filtered to remove solid impurity,
End capped polyether product is obtained, its ending ratio is 74.1%.
Embodiment 2
[embodiment 1] system is added in the tri- mouthfuls of reaction bulbs of 250mL equipped with reflux water-dividing device and the clean dried of agitator
End capped polyether 50g, the 5g hydrogen containing siloxane and 25mL toluene for obtaining, backflow are cooled to 100 DEG C after a period of time, add 5ppm chlorine
Platinic acid/ethanol solution, maintains 100 DEG C to react 3 hours.The reaction that reaction is taken out after terminating and weighed in gas decomposition apparatus is mixed
The decomposition of the sodium butoxide induction of compound sample, puts, it was demonstrated that the conversion completely of Si-H without any hydrogen release of display.
Embodiment 3
In the 2L reactors equipped with agitator, allyl alcohol polyether (EO/PO=30/70, block) 1200g is added, added
Sodium methoxide 181g, is warming up to 90~100 DEG C and reacts 2 hours, and keep simultaneously pressure in autoclave it is constant -0.08~-
0.10Mpa, vacuum removal micromolecular compound.Reaction is cooled to 40~45 DEG C after terminating, and is slowly added dropwise 402g diethyl carbonates
Afterwards, 110~120 DEG C are warming up to react 3 hours.After end, 50 DEG C are cooled to, then after neutralizing, being filtered to remove solid impurity,
End capped polyether product is obtained, its ending ratio is 72.5%.
Embodiment 4
[embodiment 3] system is added in the tri- mouthfuls of reaction bulbs of 250mL equipped with reflux water-dividing device and the clean dried of agitator
End capped polyether 50g, the 8g hydrogen containing siloxane and 25mL toluene for obtaining, backflow are cooled to 100 DEG C after a period of time, add 5ppm chlorine
Platinic acid/ethanol solution, maintains 100 DEG C to react 3 hours.The reaction that reaction is taken out after terminating and weighed in gas decomposition apparatus is mixed
The decomposition of the sodium butoxide induction of compound sample, puts, it was demonstrated that the conversion completely of SiH without any hydrogen release of display.
Embodiment 5
In the 2L reactors equipped with agitator, butylol polyether (EO/PO=50/50, random) 1000g is added, add hydrogen
Potassium oxide 82.5g, is warming up to 110~120 DEG C and reacts 2 hours, and keep simultaneously pressure in autoclave it is constant -0.08~-
0.10Mpa, vacuum removal micromolecular compound.Reaction is cooled to 40~45 DEG C after terminating, and is slowly added dropwise 132g dimethyl carbonates
Afterwards, 120~130 DEG C are warming up to react 3 hours.After end, 50 DEG C are cooled to, then after neutralizing, being filtered to remove solid impurity,
End capped polyether product is obtained, its ending ratio is 70.1%.
Embodiment 6
In the 2L reactors equipped with agitator, butylol polyether (EO/PO=35/65, block) 1200g is added, add first
Potassium alcoholate 60g, is warming up to 90~100 DEG C and reacts 3 hours, and keeps pressure in autoclave constant in -0.08~-0.10Mpa simultaneously,
Vacuum removal micromolecular compound.Reaction is cooled to 40~45 DEG C after terminating, and after being slowly added dropwise 114g diethyl carbonates, is warming up to
130~140 DEG C are reacted 4 hours.After end, 50 DEG C are cooled to, then after neutralizing, being filtered to remove solid impurity, blocked
Polyether product, its ending ratio is 76.2%.
Although embodiments of the present invention are described in detail, it should be understood that, without departing from of the invention
In the case of spirit and scope, embodiments of the present invention can be made with various changes, replace and change.
Claims (7)
1. a kind of preparation method of alkyl capped polyether, with alkyl carbonate as end-capping reagent, with poly- containing hydroxyl in strand
Ether prepares alkyl capped polyether for raw material；
The polyether structure formula containing hydroxyl is shown in (I) formula：
A[(OCH2-CHR1)x-OH]y (I)
Wherein：A is the chain radicals of C1-C20, R1It is-H, methyl or ethyl, the natural number of x=2-250, the nature of y=1-10
Number；
The alkyl capped polyether general structure is shown in (II) formula：
A[(OCH2-CHR1)x-OR2]y (II)
Wherein R2It is methyl, ethyl or phenyl；
The preparation method of the alkyl capped polyether is comprised the following steps
1) constant temperature is anti-during the polyethers containing hydroxyl of above-mentioned (I) formula at ambient temperature, is added into reactor with alkoxidation reagent
Should, while vacuum removal micromolecular compound；
2) to step 1) middle addition alkyl carbonate continuation reaction；
3) reactant obtains (II) formula structure, i.e. alkyl capped polyether by after neutralizing, filtering removal solid matter.
2. the preparation method of alkyl capped polyether according to claim 1, it is characterised in that：Step 2) alkylcarbonic acid
Ester is dimethyl carbonate, diethyl carbonate or diphenyl carbonate.
3. the preparation method of alkyl capped polyether according to claim 1, it is characterised in that：Alkoxidation reagent is hydroxide
One or more of sodium, potassium hydroxide, sodium methoxide or potassium methoxide.
4. the preparation method of alkyl capped polyether according to claim 1, it is characterised in that：Step 1) in reaction temperature 25
~120 DEG C, 0.2~5 hour reaction time, the polyethers containing hydroxyl is 1 with the molar ratio of alkoxidation reagent:1.0
~3.0.
5. the preparation method of alkyl capped polyether according to claim 1, it is characterised in that：Step 2) in reaction temperature
100~150 DEG C, 0.2~5 hour reaction time, wherein the polyethers (I) containing hydroxyl is with the molar ratio of alkyl carbonate
1:1.0~5.0.
6. the preparation method of alkyl capped polyether according to claim 1, it is characterised in that：The polyethers containing hydroxyl
Middle polyether segment is homopolymerization, random copolymerization or block copolymerization.
7. the preparation method of alkyl capped polyether according to claim 1, it is characterised in that：Step 1) in vacuum removal it is small
Vacuum pressure is -0.07~-0.10Mpa in molecular compound, and the removing time is 1~3h.
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| CN102250332A (en) * | 2011-06-09 | 2011-11-23 | 江苏天音化工有限公司 | Synthesis method of water reducing agent macromonomer methyl end capping MAOH polyoxyethylene ether |
| CN102358779A (en) * | 2011-08-04 | 2012-02-22 | 浙江皇马科技股份有限公司 | Preparation method of butyl-terminated allyl polyether |
| CN102911361A (en) * | 2011-08-03 | 2013-02-06 | 赢创高施米特有限公司 | Alkyl carbonate end-capped polyethersiloxanes and method for its manufacture |
-
2016
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102250332A (en) * | 2011-06-09 | 2011-11-23 | 江苏天音化工有限公司 | Synthesis method of water reducing agent macromonomer methyl end capping MAOH polyoxyethylene ether |
| CN102911361A (en) * | 2011-08-03 | 2013-02-06 | 赢创高施米特有限公司 | Alkyl carbonate end-capped polyethersiloxanes and method for its manufacture |
| CN102358779A (en) * | 2011-08-04 | 2012-02-22 | 浙江皇马科技股份有限公司 | Preparation method of butyl-terminated allyl polyether |
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Application publication date: 20170613 |