CN85108553A - The method for preparing polytetramethylene glycol - Google Patents
The method for preparing polytetramethylene glycol Download PDFInfo
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- CN85108553A CN85108553A CN85108553.9A CN85108553A CN85108553A CN 85108553 A CN85108553 A CN 85108553A CN 85108553 A CN85108553 A CN 85108553A CN 85108553 A CN85108553 A CN 85108553A
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 12
- -1 polytetramethylene Polymers 0.000 title claims abstract description 9
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 title claims abstract description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 70
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000003999 initiator Substances 0.000 claims abstract description 20
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910015900 BF3 Inorganic materials 0.000 claims abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 5
- 230000001105 regulatory effect Effects 0.000 claims abstract description 3
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims abstract 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 230000009466 transformation Effects 0.000 description 19
- 229920000642 polymer Polymers 0.000 description 8
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- USHBCJKLMPPLOX-UHFFFAOYSA-N acetyl acetate;perchloric acid Chemical compound OCl(=O)(=O)=O.CC(=O)OC(C)=O USHBCJKLMPPLOX-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000012656 cationic ring opening polymerization Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Substances OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Polyethers (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The method for preparing polytetramethylene glycol belongs to the tetrahydrofuran by polymerization field.Solve the problem of now using the initiator severe corrosion equipment.Characteristics are: with boron trifluoride is initiator, having at least epoxy chloropropane to exist and in anhydrous or have under the condition of water, in below 10 ℃, be preferably in 0 °～5 ℃, make tetrahydrofuran by polymerization, polymerization time is 5 minutes to 24 hours, add the entry termination reaction, a step forms the polytetramethylene glycol that the chain two ends are all hydroxyl, and molecular-weight average is below 20000, particularly molecular weight can be regulated below 3000.Technology of the present invention is simple, convenient post-treatment, and initiator corrodibility is low, the product yield height.
Description
Polytetramethylene glycol is to be formed by cationic ring-opening polymerization by tetrahydrofuran (THF) (THF), is to produce block polyether polyurethane and the elastomeric important soft section material of polyether polyester, requires its molecular weight to be lower than 3000, and is adjustable, and the two ends of chain all must be hydroxyls.The industrial process that can satisfy above-mentioned condition at present have three kinds (Chemical Industry Inst. of Hunan Prov., the Hunan chemical industry, 1975(1), 81.Zhang Hongzhi, Dong Xiuzhi, Feng Xinde, polymer communication, 1978,119.）。One, aceticanhydride-perchloric acid is the initiator system method.The product end group that this method single step reaction generates is an ethanoyl, needs carry out saponification in alcohol, and flow process is more numerous, and still residual 0.5～1.0% acetyl end group (Japan's special permission, clear 48-32200) in the sample after the saponification; In addition, aceticanhydride consumption height (be monomeric charge amount 20%) is strong to equipment corrosion.Two, fluosulfonic acid is made the initiator method.The difficult preparation of this method initiator, consumption also big (be about monomeric charge amount 8～15%), serious to equipment corrosion.Three, be the initiator system method with oleum-perchloric acid.Though the initiator price of this method is lower, corrodibility is strong.More than three kinds of methods all equipment is had the deep-etching effect, bring difficulty to production.
The present invention adopts boron trifluoride to make initiator, and its corrodibility is lower, is applicable to industrial production.Johnston (Johnston, P.R., J.Appl, Polym, sci., 1965,9,461; US 3,359,332, (1967)) once used 5%(mol) boron trifluoride ethyl ether complex (BF
3OEt
2) and the initiator system formed of promotor oxyethane (EO) cause the THF polymerization, through reaction in 17 minutes, transformation efficiency was 17%, molecular weight of product is 1000; Reacted 34 minutes, then transformation efficiency reaches 34%, and molecular weight is 2000.The molecular weight of product is controlled in the Johnston suggestion with the reaction times.But owing to the change with transformation efficiency, the molecular weight of product floating range is excessive, is difficult for being controlled by the time, thereby is not accepted.
It is difficult to cause the THF polymerization with boron trifluoride separately.So share, normal and propylene oxide (PO), oxyethane or epoxy chloropropane small molecules three-membered ring ethers (doing promotor) such as (ECH) causes the THF polymerization.Initiation reaction has not only been accelerated in the effect of promotor, and can improve efficiency of initiation.It is generally acknowledged with EO and ECH be the promotor effect than good with PO, but between EO and ECH, do not do further relatively.People such as Saegusa (Saegusa, T., Matsumoto, S., Macromol, 1968,1,442) and people (Fujimoto such as Fujimoto, T., Kawahashi, M., Nagasawa, M., Takahashi, A., Polym, J., 1979.11,193) experimental data shows respectively, and when 0 ℃ was promotor with ECH or EO, polymerization did not have chain termination and chain transfer reaction.Therefore, can generate the polyether products that the chain two ends are hydroxyl in polymerization later stage water termination reaction.To the reaction of no chain termination and chain transfer, have formula (1) (Zhang Hongzhi, Dong Jiayang, Wang Yanle, Ceng Xiansen, Feng Xinde, polymer communication .1985(4) 258) relation:
Molecular-weight average (MW)=(transformation efficiency * monomer density * 1000)/(initiator concentration * I
f) (1)
I wherein
fBe efficiency of initiation; Initiator concentration unit be mole (mol) initiator concentration not very big (as under＜5mol%) the situation, the molecular weight that control product 3000 with next transformation efficiency and I
fTwo play a decisive role.Work as I
fWhen low, only just can make molecular-weight average low under the situation of low-conversion, can only be that to make molecular weight of product at 17% o'clock be 1000 at transformation efficiency as Johnston.And molecular weight of product is unsteady bigger with transformation efficiency when low-conversion, rises at 34% o'clock as transformation efficiency, and molecular weight promptly increases to 2000.
We find, if change promotor into ECH, and I then
fCan significantly improve.Can see by table 1, when concentration of initiating system strengthens, I
fValue reduces; And under close concentration, be then I of promotor with ECH
fValue is about 1.5～5 times when the EO, and therefore selecting ECH for use is promotor, when transformation efficiency still can make molecular weight of product at the polymkeric substance below 3000 up to 70～80% the time.And molecular weight of product unsteady less with rate of rotation, as work as I
fBe that the data of trying to achieve by formula (1) in 0.5 o'clock show (seeing Table 2), when polymerisation conversion increases to 80% the time by 70%, molecular weight only increases to 2368 by 2072.Such molecular weight can satisfy the requirement of industrial preparation polytetramethylene glycol basically with the rangeability of transformation efficiency.
*Try to achieve by formula (1); △ (Johnston, P.R., J.Appl.Pelym.Scl., 1965,9,46])
Can in reaction system, add molecular weight regulator for further strictly controlling molecular weight of product, as water, aceticanhydride, dibasic alcohol etc.We find that water can be controlled molecular weight effectively.When doing water, generally be limited in BF on the document to the research of THF polymerization influence
3: H
2O is 1: a 0～1(mol ratio) with interior (Kuzaev.A.I., Komratov, G.N., Korovina, G.V., Entelis, S.G., Vysokom.Soed.A, 1970,12,1033; Rozenberg, B.A., Liudvig, E.B., Gantmaher, A.R., Medvedev, S.S.Vysokom.Soed.1964,6,2035), and THF polymerization well when pointing out that the water yield is big, because water is the polymeric terminator.And work as water consumption after a little while, the phenomenon of molecular weight unexpected rapid increase can occur with the carrying out (being about at 40% o'clock) of polyreaction, thereby be difficult to control the molecular weight of product with the rising of rate of rotation as transformation efficiency.
It is BF that the present invention adopts the water yield to be a bit larger tham 1: 1
3: H
2O is 1: 1.05-2, be preferably 1: 1.20-1.35, obtained comparatively satisfied polymerisation conversion, and overcome the phenomenon that molecular weight sharply increases, make the molecular weight of product obtain control (seeing Table 6) more strictly, promptly molecular weight of product further dwindles during than polymerization under anhydrous condition with the floating range of polymerisation conversion.
The initiator boron trifluoride can directly use, and perhaps uses itself and tetrahydrofuran (THF) (BF
3THF) or the complex compound that forms of ether, two kinds of complex compounds, gained result close (seeing Table 4); Temperature during polymerization is being less than or equal to 10 ℃, and is best (seeing Table 7) with 0～5 ℃.The molecular-weight average of product is lower than 20000, and particularly molecular weight can regulated below 3000; The both-end of polymeric chain is hydroxyl (seeing Table 3); The infrared spectra consistent (Hummel, D.O., Infraed Analysis of Polymers, Resins and Additives, Wiley-Inferscience, New york, 1969, Vol.1,985) of polytetramethylene glycol on the infrared spectra of product and the handbook
〉
In order to further specify the present invention, enumerate following example
Example 1. in 100ml be equipped with three mouthfuls of electronic stirring and in add 50ml(0.625mol) THF, put into 2 ℃ of thermostatic baths, cool off 10 minutes, adding 0.0313mol(is the 5.0mol% that THF measures) BF
3.OEt
2And 0.0313molECH.Start stirring, the suitable thickness of system after 10 minutes adds 6-8ml water termination reaction, stirs to add 75ml water again after 5 minutes.Heating steams unreacted THF under slowly stirring.The distillate that weighing is collected is by THF content one refractive index (n
25.0 D) figure measures wherein THF content, calculates the THF yield.Remaining reaction solution, the water of branch sub-cloud is used 5%Na respectively
2CO
2The aqueous solution and washed several times with water.Polymer fluid is transferred in the flask, and in 100 ℃, underpressure distillation dehydration under 20～40mm mercury column is not dewatered half an hour after bubble produces to having again, and product is the water white transparency viscous fluid, and transformation efficiency 68.2%, ultimate yield are 88.8%, M
GpcBe 1.8 * 10
3In benzene and alcohol mixeding liquid (volume ratio is 1: 1), be 0.19mgKOH/g with 0.02N potassium hydroxide-ethanol measured in solution acid number.
Polymerisation conversion=(resulting polymers weight/THF feeds intake heavily) * 100%.Ultimate yield=(resulting polymers heavily/(THF feeds intake weight-recovery THF heavily)) * 100%.
Example 2. adds 100ml(1.25mol in the 250ml there-necked flask that electronic stirring is housed) THF, put into 2 ℃ of thermostatic baths, start stirring, cooled off 10 minutes.Add 0.0641mol water, 0.0301molBF
3.OEt
2(for the 4.0mol% of THF amount) and 0.0501molECH.The system of reacting after the 6 or 10 hours suitable thickness that become adds the water termination reaction, its operation and post-processing operation and example 1 with.Reacting 10 hours polymerisation conversions is 57.9%, and ultimate yield is 92.8%, M
GpcBe 2.0 * 10
3, acid number is 0.23mgKOH/g, and product is the water white transparency thick liquid, and the soft wax shape becomes colorless after long-time the placement.During 6 hours termination reactions of polymerization, transformation efficiency is 59.6%, M
GpcBe 1.9 * 10
3Illustrate polymerization 6 hours with 10 hours, the two result is close.
Example 3. in test tube with 5ml(0.0625mol) THF is chilled to-10 ℃, adds BF
3THF0.00312mol(is the 5.0mol% of THF amount) and ECH0.00363mol.Filled drying nitrogen about one minute, the jam-pack soft rubber ball shakes up, and inserts polymerization in 2 ℃ of thermostatic baths, and system becomes sticky thick gradually.The mixed solution termination reaction that adds 3ml THF and 0.5ml water after 10 minutes.Shook 5～10 minutes, add 7.5ml water again, in boiling water bath, boil off THF, be dissolved in the 5ml hexanaphthene after cold, wash with water 4～5 times, drying under reduced pressure, 20～40mm mercury column that reduces pressure gradually, temperature is 60-80 ℃, continued dry 1 hour, get the water white transparency viscous fluid, polymerisation conversion is 59.0%, M
GpcBe 1.57 * 10
3
Use BF
3OEt
2Replace BF
3THF obtains similar result (seeing Table 4).Reduce initiator amount, molecular weight of product increases, and therefore can regulate the molecular weight of product with the initiator different amounts.
Example 4. adds 50ml(0.625mol in the 100ml there-necked flask) THF, 0.0317mol(is the 5.1mol% of THF amount) BF
3THF and 0.0313molECH.By the operation of example 1, must table 5 in different polymerization time termination reactions, illustrate that molecular weight of product is less with the unsteady of transformation efficiency.
Example 5. is chilled to-10 ℃ with 5ml THF in test tube, add BF
3THF, ECH and water, in 2 ℃ of polymerizations, through the different time termination reaction, can try to achieve is having under the water condition polymer molecular weight with the unsteady situation (seeing Table 6) of transformation efficiency.Work as BF
3: H
2O(mol) be at 1: 1.23～1.31 o'clock, transformation efficiency increases 12%～13%, and molecular weight of product is almost constant, illustrate that water has played the effect of molecular weight regulator, but water consumption molecular weight unsteady bigger with transformation efficiency after a little while.Polymerization and post-processing operation and example 3 are together.
Example 6. changes BF
3And the consumption and the polymerization temperature of water, polymerization and post-processing operation must tables 7 with example 5.The consumption of initiator or water strengthens molecular weight of product is descended.The increase of water consumption is also led transformation efficiency and is descended.Select for use the suitable amounts of initiator and water can more strictly regulate the molecular weight of product.In addition, when polymerization temperature adopted 2 ℃ or 5 ℃, the gained result was close, but then transformation efficiency and molecular weight all obviously descend in 10 ℃ of polymerizations.
Claims (3)
1, a kind of method that makes tetrahydrofuran by polymerization, it is characterized in that, make initiator with boron trifluoride, having at least in the presence of the epoxy chloropropane, be less than or equal to 10 ℃, be preferably in 0 °～5 ℃ polymerizations, polymerization time is 5 minutes to 24 hours, adds the entry termination reaction, and a step forms the polytetramethylene glycol that the chain two ends are all hydroxyl, molecular-weight average is below 20000, and particularly molecular weight can regulated below 3000.
2,, it is characterized in that used initiator is the complex compound of boron trifluoride and tetrahydrofuran (THF) or ether formation according to claim 1.
3, according to claim 1 or 2, it is characterized in that, anhydrous or add polymerization under the situation of entry, the mol ratio (H of the water yield of adding and boron trifluoride amount
2O: BF
3) be 1.05-2: 1, be preferably 1.20-1.35: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85108553.9A CN1005720B (en) | 1985-11-27 | 1985-11-27 | Method for producing polytetramethylene glycol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85108553.9A CN1005720B (en) | 1985-11-27 | 1985-11-27 | Method for producing polytetramethylene glycol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85108553A true CN85108553A (en) | 1987-06-03 |
| CN1005720B CN1005720B (en) | 1989-11-08 |
Family
ID=4796070
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85108553.9A Expired CN1005720B (en) | 1985-11-27 | 1985-11-27 | Method for producing polytetramethylene glycol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1005720B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1131254C (en) * | 1996-07-11 | 2003-12-17 | 旭化成株式会社 | Boron trifluoride complex for polymerization of trioxane |
| CN115725066A (en) * | 2022-11-15 | 2023-03-03 | 河南省生物基材料产业研究院有限公司 | Preparation method of bio-based polytetrahydrofuran |
-
1985
- 1985-11-27 CN CN85108553.9A patent/CN1005720B/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1131254C (en) * | 1996-07-11 | 2003-12-17 | 旭化成株式会社 | Boron trifluoride complex for polymerization of trioxane |
| CN115725066A (en) * | 2022-11-15 | 2023-03-03 | 河南省生物基材料产业研究院有限公司 | Preparation method of bio-based polytetrahydrofuran |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1005720B (en) | 1989-11-08 |
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