CN109306053A - Small molecule polyether polyol efficiently synthesizes new process - Google Patents
Small molecule polyether polyol efficiently synthesizes new process Download PDFInfo
- Publication number
- CN109306053A CN109306053A CN201811131013.7A CN201811131013A CN109306053A CN 109306053 A CN109306053 A CN 109306053A CN 201811131013 A CN201811131013 A CN 201811131013A CN 109306053 A CN109306053 A CN 109306053A
- Authority
- CN
- China
- Prior art keywords
- polyether polyol
- added
- small molecule
- epoxyalkane
- new process
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000570 polyether Polymers 0.000 title claims abstract description 55
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 52
- 229920005862 polyol Polymers 0.000 title claims abstract description 40
- 150000003077 polyols Chemical class 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 28
- 150000003384 small molecules Chemical class 0.000 title claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 15
- 230000006698 induction Effects 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- 230000032683 aging Effects 0.000 claims abstract description 7
- 230000018044 dehydration Effects 0.000 claims abstract description 7
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 7
- 238000010792 warming Methods 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000000977 initiatory effect Effects 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 3
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 150000005846 sugar alcohols Polymers 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- 125000002947 alkylene group Chemical group 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- 230000001939 inductive effect Effects 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 230000002194 synthesizing effect Effects 0.000 abstract description 6
- 239000003999 initiator Substances 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 3
- 238000007664 blowing Methods 0.000 abstract description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 24
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000009825 accumulation Methods 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- -1 Oxygen alkane Chemical class 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/2645—Metals or compounds thereof, e.g. salts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/329—Phosphorus containing acids
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
Abstract
The invention belongs to polymer synthesis techniques fields, and in particular to a kind of small molecule polyether polyol efficiently synthesizes new process.Small molecule polyether polyol is added to polymerization reaction kettle, catalyst and acid regulator is added, it is warming up to 100~130 DEG C of 1~2h of dehydration, then epoxyalkane is added and carries out induction initiation reaction, after induction period, the mixture for being continuously added to small molecular alcohol and epoxyalkane in proportion carries out polymerization reaction, charging is further continued for a certain amount of epoxyalkane is added after finishing to be continued to polymerize, 0.5~1h of aging reaction after charging, 100~110 DEG C are cooled to vacuumize 0.5~1 hour, antioxidant and acid regulator is added, after mixing evenly blowing.The technique efficiently solve bimetallic catalyst can not direct catalytic small molecule initiator synthesizing polyether technical bottleneck, realize the technological break-through of bimetallic catalyst synthesized micromolecule polyether polyol, with short production cycle, no waste water and dregs generate, and product yield is high.
Description
Technical field
The invention belongs to polymer synthesis techniques fields, are specifically related to a kind of efficiently synthesizing for small molecule polyether polyol
New process.
Background technique
Polyether polyol is to prepare one of main raw material(s) of polyurethane material, is dosage maximum one in polyurethane material
Class chemical raw material.Currently, the technology for producing of polyether polyol is highly developed, low molecular polyether, high-molecular-weight poly
Ether, high functionality polyethers, high activity polyether, flame retarding polyether etc. various types of polyethers can be prepared.In polyethers synthesis at present
According to the difference of catalyst system, mainly including KOH catalyst system, amines catalysis system and Bimetallic catalyst system three categories, often
A kind of catalyst respectively has feature, and small-molecular-weight, middle high molecular weight high activity polyether can be achieved in KOH catalyst system in synthesizing polyether
Synthesis, but the disadvantage is that catalytic activity is relatively low, and be related to aftertreatment technology, the three wastes generate more, and equipment investment is big, produces
Low efficiency；Amines catalysis system be suitble to rigid-foam polyether polyol synthesis, catalytic activity is lower, can not prepare in high-molecular-weight poly
Ethoxylated polyhydric alcohol；Bimetallic catalyst system catalytic activity is very high, and side reaction is few, and the polyether polyol of preparation has molecule
The characteristics of amount is high, narrowly distributing, as patent CN201310628896 is mentioned using DMC catalyzed preparation of poly ethoxylated polyhydric alcohol, but it is mentioned
The method of confession can only prepare high molecular weight polyether, its maximum restricts is exactly that cannot achieve in currently practical industrial application
Low molecule weight initiator direct polymerization prepares small-molecular-weight polyether polyol, equipment investment is low, advantage of high production efficiency
To comprehensive release, this is also existing technical problem in current industry.
Summary of the invention
The purpose of the present invention is overcome the deficiencies of the prior art and provide a kind of efficiently synthesizing newly for small molecule polyether polyol
Technique.The synthesis technology efficiently solve bimetallic catalyst can not direct catalytic small molecule initiator synthesizing polyether technology bottle
Neck realizes the technological break-through of bimetallic catalyst synthesized micromolecule polyether polyol, with short production cycle, no waste water, waste residue
It generates, product yield is high.
Small molecule polyether polyol of the present invention efficiently synthesizes new process, specifically by small molecule polyether polyol
It is added to polymerization reaction kettle, catalyst and acid regulator is added, is warming up to 100~130 DEG C of 1~2h of dehydration, ring is then added
Oxygen alkane carries out induction initiation reaction, after induction period, starts the mixing for being continuously added to small molecular alcohol and epoxyalkane in proportion
Object carries out polymerization reaction, and charging is further continued for a certain amount of epoxyalkane is added after finishing to be continued to polymerize, aging after charging
0.5~1h is reacted, 100~110 DEG C is cooled to and vacuumizes 0.5~1 hour, antioxidant and acid regulator is added, stirs evenly
Blowing afterwards.
Wherein:
Small molecule polyether polyol for originating reaction is 2 degrees of functionality or 3 degrees of functionality of the molecular weight 200~500
Polyether polyol, which is catalyzed and synthesized using alkali metal catalyst system, specifically use KOH catalyst, potassium from
Sub- content requirement≤5ppm；One in the preferred propylene glycol polyether polyol of small molecule polyether polyol or glycerin polyether polyalcohol
Kind.
Catalyst is bimetallic cyanide complex catalyst, i.e. dmc catalyst；Catalyst amount is that polymeric articles are total
20~100ppm of quality.
Polymeric articles gross mass is exactly the gross mass for all raw materials being added in the reaction process for prepare target product
With.
Acid regulator is one or both of citric acid, adipic acid, phosphoric acid, acetic acid or sulfuric acid；Dosage is polymer
10~50ppm of product gross mass.
For induce initiation reaction epoxyalkane quality be reaction process in be added epoxyalkane gross mass 2~
6%.
The polymerization temperature of polymerization stage is controlled at 130~145 DEG C.
After induction period, the small molecular alcohol of addition and the mass ratio of epoxyalkane are 1:4~1:15.Small molecular alcohol preferably third
Two pure and mild glycerol.
Epoxyalkane is the mixture of propylene oxide (PO) or propylene oxide (PO) and ethylene oxide (EO).
The mass ratio of propylene oxide and ethylene oxide is 70~100:30~0.
Charging is further continued for a certain amount of epoxyalkane is added after finishing to be continued to polymerize, and it is anti-that the quality of epoxyalkane, which is added,
The 2%~10% of the epoxyalkane gross mass that should be added in the process.
Compared with the prior art, the present invention has the following beneficial effects:
(1) polymerization technique realizes the technological break-through of dmc catalyst catalytically synthesizing small molecular polyether polyol, breaks
Dmc catalyst is only used for the traditional idea of synthesis high molecular weight polyether；The small molecule polyether polyol items physical property of preparation refers to
Mark is essentially identical with the index of tradition KOH Catalytic processes, and molecular weight distribution is essentially identical.
(2) since the catalyst of this synthesis technology use is high-efficient, product is without neutralization, drying, absorption, filtering
Etc. cumbersome postprocessing working procedures, equipment investment is few, and the production cycle substantially shortens nearly 80%, and entire synthesis process does not have waste water, gives up
The generation of slag, yield can reach 99.5% or more, and high-efficiency environment friendly has good economic value.
Detailed description of the invention
Fig. 1 is traditional 400 molecular weight polyether polyol GPC spectrogram of KOH Catalytic processes；
Fig. 2 is the 400 molecular weight polyether polyol GPC spectrograms using the preparation of herein described technique.
Specific embodiment
The invention will be further described with reference to embodiments.
Embodiment 1
The concentrated sulfuric acid of the propylene glycol polyether polyol of 80Kg molecular weight 200, the dmc catalyst of 40g, 8g are added to pressure resistance
In reaction kettle, nitrogen is replaced to oxygen content 50ppm, is warming up to 130 DEG C, and vacuum degree -0.093MPa is kept to vacuumize dehydration 1.5h；
The PO that 12Kg is added carries out induced activation reaction, when being decreased obviously occurs in reacting kettle inner pressure, temperature in the kettle steeply rises, table
Bright polymerization reaction starts, and is continuously added to propylene glycol by proportional controller and PO is polymerize, and polymeric reaction temperature is controlled 143
It ± 2 DEG C, after propylene glycol accumulation charging 45.6Kg, PO accumulation charging 255.4Kg, then is continuously added to the PO of 7Kg and continues to polymerize
Reaction after charging, continues aging reaction 40min, and pressure tends to balance, is cooled to 100 DEG C, vacuumizes demonomerization 0.5h,
240g antioxidant 1076 and 5g phosphoric acid is added, stirring 20min discharging is sealed, and discharge 398.5Kg in total, total production cycle
10h, yield 99.55%.
Embodiment 2
The propylene glycol polyether polyol of 80Kg molecular weight 400, the dmc catalyst of 21g, 20g adipic acid are added to pressure resistance
In reaction kettle, nitrogen is replaced to oxygen content 50ppm, is warming up to 120 DEG C, and vacuum degree -0.093MPa is kept to vacuumize dehydration 1h；Add
The PO/EO mixture (mass ratio PO/EO=85/15) for entering 13Kg carries out induced activation reaction, when reacting kettle inner pressure appearance is bright
When aobvious decline, temperature in the kettle steeply rise, show that polymerization reaction starts, by proportional controller be continuously added to propylene glycol, PO and
EO is polymerize, polymeric reaction temperature control at 132 ± 2 DEG C, propylene glycol accumulation charging 60.8Kg, PO accumulation charging 444.7Kg,
After EO accumulation charging 78.5Kg, then by the EO that proportional controller is continuously added to the PO and 3.45Kg of 19.55Kg continue to gather
Reaction to be closed, after charging, continues aging reaction 1h, pressure tends to balance, is cooled to 105 DEG C, vacuumizes demonomerization 40min,
400g antioxidant 1076 and 8g phosphoric acid is added, stirring 20min discharging is sealed, and discharge 697.6Kg in total, total production cycle
10.5h, yield 99.6%.
Embodiment 3
The glycerin polyether polyalcohol of 150Kg molecular weight 500, the dmc catalyst of 60g, 10g citric acid are added to pressure-resistant anti-
It answers in kettle, nitrogen is replaced to oxygen content 50ppm, is warming up to 130 DEG C, and vacuum degree -0.093MPa is kept to vacuumize dehydration 2h；It is added
The PO of 19Kg carries out induced activation reaction, when being decreased obviously occurs in reacting kettle inner pressure, temperature in the kettle steeply rises, shows to gather
It closing reaction to start, glycerol is continuously added to by proportional controller and PO is polymerize, polymeric reaction temperature is controlled at 140 ± 2 DEG C,
It after glycerol accumulation charging 64.4Kg, PO accumulation charging 688.6Kg, then is continuously added to the PO of 78Kg and continues polymerization reaction, add
After material, continue aging reaction 40min, pressure tends to balance, is cooled to 110 DEG C, vacuumizes demonomerization 1h, and it is anti-that 600g is added
Oxygen agent 1076 and 10g phosphoric acid, stirring 20min discharging are sealed, and discharge 998.1Kg in total, total production cycle 10.2h, yield
99.74%.
Comparative example 1
The KOH of the propylene glycol of 76Kg and 1Kg is added in pressure-resistant reaction kettle, nitrogen is replaced to oxygen content 50ppm, heating
Start PO charging when to 80 DEG C, be warming up to 115 DEG C in charging, maintains PO continuous feed at a temperature of this, pressure control≤
After 0.25MPa, PO 324Kg are fed, continue aging reaction 4h, pressure no longer declines, and vacuumizes demonomerization 0.5h, cools down
To≤90 DEG C, the phosphoric acid of 85% concentration of 2.05Kg and the pure water of 16Kg is added to kettle is post-processed in liquid relief, neutralization reaction 1.5h,
Then the magnesium silicate adsorbent of 0.4Kg is added, stirs 0.5h, then heats to 105 DEG C and vacuumizes dehydration and drying, timing 8 hours,
After sample detection moisture is qualified, circulating filtration 1h is carried out, after sample detection is qualified, discharge is sealed, and discharge 390Kg in total,
Total production cycle 45.2h, yield 97.5%.
Physical index test is carried out to small molecule polyether polyol made from embodiment 1-3 and comparative example 1 respectively, test refers to
Mark is shown in Table 1.
1 small molecule polyether polyol physical index test result of table
Claims (10)
1. a kind of small molecule polyether polyol efficiently synthesizes new process, it is characterised in that: small molecule polyether polyol to be added
To polymerization reaction kettle, catalyst and acid regulator is added, is warming up to 100~130 DEG C of 1~2h of dehydration, alkylene oxide is then added
Hydrocarbon carries out induction initiation reaction, after induction period, start to be continuously added in proportion the mixture of small molecular alcohol and epoxyalkane into
Row polymerization reaction, charging is further continued for a certain amount of epoxyalkane is added after finishing to be continued to polymerize, aging reaction after charging
0.5~1h is cooled to 100~110 DEG C and vacuumizes 0.5~1 hour, and antioxidant and acid regulator is added, puts after mixing evenly
Material.
2. small molecule polyether polyol according to claim 1 efficiently synthesizes new process, it is characterised in that: for originating
The small molecule polyether polyol of reaction is molecular weight in 200~500 2 degrees of functionality or the polyether polyol of 3 degrees of functionality, this is poly-
Ethoxylated polyhydric alcohol is synthesized using KOH catalyst, potassium content requirement≤5ppm.
3. small molecule polyether polyol according to claim 1 efficiently synthesizes new process, it is characterised in that: catalyst is
Bimetallic cyanide complex catalyst；Catalyst amount is 20~100ppm of polymeric articles gross mass.
4. small molecule polyether polyol according to claim 1 efficiently synthesizes new process, it is characterised in that: acidity is adjusted
Agent is one or both of citric acid, adipic acid, phosphoric acid, acetic acid or sulfuric acid；Dosage be polymeric articles gross mass 10~
50ppm。
5. small molecule polyether polyol according to claim 1 efficiently synthesizes new process, it is characterised in that: for inducing
The quality of the epoxyalkane of initiation reaction is the 2~6% of the epoxyalkane gross mass being added in reaction process.
6. small molecule polyether polyol according to claim 1 efficiently synthesizes new process, it is characterised in that: polymerization reaction
The polymerization temperature in stage is controlled at 130~145 DEG C.
7. small molecule polyether polyol according to claim 1 efficiently synthesizes new process, it is characterised in that: induction period mistake
Afterwards, the mass ratio of the small molecular alcohol and epoxyalkane of addition is 1:4~1:15.
8. small molecule polyether polyol according to claim 1 efficiently synthesizes new process, it is characterised in that: epoxyalkane
For propylene oxide or the mixture of propylene oxide and ethylene oxide.
9. small molecule polyether polyol according to claim 8 efficiently synthesizes new process, it is characterised in that: propylene oxide
Mass ratio with ethylene oxide is 70~100:30~0.
10. small molecule polyether polyol according to claim 1 efficiently synthesizes new process, it is characterised in that: fed
It is further continued for a certain amount of epoxyalkane is added after finishing and continues to polymerize, the quality that epoxyalkane is added is to be added in reaction process
The 2%~10% of epoxyalkane gross mass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811131013.7A CN109306053A (en) | 2018-09-27 | 2018-09-27 | Small molecule polyether polyol efficiently synthesizes new process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811131013.7A CN109306053A (en) | 2018-09-27 | 2018-09-27 | Small molecule polyether polyol efficiently synthesizes new process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109306053A true CN109306053A (en) | 2019-02-05 |
Family
ID=65224083
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811131013.7A Pending CN109306053A (en) | 2018-09-27 | 2018-09-27 | Small molecule polyether polyol efficiently synthesizes new process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109306053A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110818889A (en) * | 2019-11-15 | 2020-02-21 | 山东蓝星东大有限公司 | Synthesis method of micromolecular polyether polyol with narrow molecular weight distribution |
| WO2022160078A1 (en) * | 2021-01-26 | 2022-08-04 | 万华化学集团股份有限公司 | Induction system for epoxide continuous polymerization, inducer, and method for epoxide continuous polymerization |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105008428A (en) * | 2013-03-14 | 2015-10-28 | 拜耳材料科学有限公司 | Improved continuous process for the production of low molecular weight polyethers with a dmc catalyst |
| CN107200837A (en) * | 2016-03-18 | 2017-09-26 | 淮安巴德聚氨酯科技有限公司 | A kind of method that utilization dmc catalyst circulation prepares PPG |
| CN107936241A (en) * | 2017-11-27 | 2018-04-20 | 山东诺威新材料有限公司 | Polyethers for defoamer and preparation method thereof |
-
2018
- 2018-09-27 CN CN201811131013.7A patent/CN109306053A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105008428A (en) * | 2013-03-14 | 2015-10-28 | 拜耳材料科学有限公司 | Improved continuous process for the production of low molecular weight polyethers with a dmc catalyst |
| CN107200837A (en) * | 2016-03-18 | 2017-09-26 | 淮安巴德聚氨酯科技有限公司 | A kind of method that utilization dmc catalyst circulation prepares PPG |
| CN107936241A (en) * | 2017-11-27 | 2018-04-20 | 山东诺威新材料有限公司 | Polyethers for defoamer and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110818889A (en) * | 2019-11-15 | 2020-02-21 | 山东蓝星东大有限公司 | Synthesis method of micromolecular polyether polyol with narrow molecular weight distribution |
| WO2022160078A1 (en) * | 2021-01-26 | 2022-08-04 | 万华化学集团股份有限公司 | Induction system for epoxide continuous polymerization, inducer, and method for epoxide continuous polymerization |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108070082B (en) | Method for preparing low-viscosity high-molecular-weight polyether polyol | |
| JP5042224B2 (en) | Method for producing polyether alcohol | |
| US10479863B2 (en) | Method for cyclically preparing polyether polyol by using DMC catalyst | |
| CN109369903B (en) | Preparation method of fatty alcohol polyether | |
| CN106810682B (en) | The preparation method of rigid-foam polyether polyol | |
| CN110922580A (en) | Preparation method of high molecular weight high activity polyether polyol | |
| CN109306053A (en) | Small molecule polyether polyol efficiently synthesizes new process | |
| CN103586067B (en) | Method for synthesizing acrylic acid by aqueous formaldehyde solution and acetic acid | |
| CN110551278B (en) | Supported catalyst and preparation method and application thereof | |
| CN107151318A (en) | Sucrose polyethers polyalcohol and preparation method thereof | |
| CN106750241A (en) | The preparation method of the allyl polyether polyalcohol of secondary hydroxyl end-blocking | |
| CN107056670B (en) | A kind of preparation method of two tertiary base peroxide | |
| CN102585199B (en) | Method for preparing polyether polyol | |
| CN113354806B (en) | Epoxy-terminated allyl alcohol polyether and preparation method thereof | |
| CN203018083U (en) | Reactor applicable to polyurethane heat-insulating adhesive production | |
| CN104530410B (en) | A kind of high molecular weight unsaturated polyether polymeric monomer and its preparation method and application | |
| CN110408018A (en) | A kind of ternary composite metal oxide solid base catalyst and its preparation method and application | |
| CN112679721B (en) | Preparation method of high-molecular-weight low-viscosity sorbitol-based polyether polyol and obtained polyether polyol | |
| CN103709392B (en) | The preparation method of polyether polyol for automobile sealant | |
| CN101914200A (en) | Method for preparing allyl polyoxyethylene ether | |
| CN107903387A (en) | The method for improving polyether polyol building-up process oxypropylene conversion ratio | |
| CN115850683B (en) | Preparation process of refined polyether suitable for textile auxiliary | |
| CN115403757B (en) | Continuous production method of polycarboxylate water reducer polyether monomer | |
| CN102719611A (en) | Nitrogen increasing method for stainless steel | |
| MX2007015048A (en) | Continuous processes for the production of alkylphenol ethoxylates . |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190205 |