CN1175596A - Boron trifluoride complex for polymerization of trioxane - Google Patents
Boron trifluoride complex for polymerization of trioxane Download PDFInfo
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- CN1175596A CN1175596A CN97114654A CN97114654A CN1175596A CN 1175596 A CN1175596 A CN 1175596A CN 97114654 A CN97114654 A CN 97114654A CN 97114654 A CN97114654 A CN 97114654A CN 1175596 A CN1175596 A CN 1175596A
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- Prior art keywords
- boron trifluoride
- complex
- organic compound
- trioxane
- solution
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention relates to a boron trifluoride complex compound solution for polymerization of trioxane. This solution comprises (A) a boron trifluorine complex compound of boron trifluoride with an organic compound and (B) a free organic compound capable of forming a complex compound with boron trifluoride component, but not forming the complex compound and forms complex compound solition comprising boron trifluoride and contains the boron trifluoride component in an amount of <=0.98mol based on 1mol total organic compound. Furthermore, the invetion also relates to a method of polymerization or copolymerization of trioxane by using said complex compound solition comprising boron trifluoride as a catalyzer.
Description
The present invention relates to boron trifluoride complex, relate in the copolyreaction of the homopolymerization of trioxane or itself and cyclic ethers, have the boron trifluoride complex of good especially operation stability in more detail.
Boron trifluoride is widely used for organic reactions such as alkylated reaction, condensation reaction, rearrangement reaction, cyclization always, also can be used as the catalyzer of various polyreactions.
Boron trifluoride is colourless non-combustible gas at normal temperatures and pressures, can be directly uses with gaseous state, also can use with it and the complex form that the organism that contains oxygen etc. forms.Can alcohol, ether, acid, ester etc. be arranged with the oxygen containing organic compound that boron trifluoride forms title complex, methyl alcohol, ethanol, phenol, acetic acid, diethyl ether, di-n-propyl ether, di-n-butyl ether etc. are specifically arranged.
From academic aspect these Substance Properties were carried out research already.For example, for forming title complex with boron trifluoride, organic compound is compared with boron trifluoride should be excessive, have the people to the infrared absorption of the excessive solution of this organic compound carried out studying (Zh.Fiz.Khim. (1967), 41, (11), 2772-6); Also have the research that the chemical shift of pair boron trifluoride complex carries out (Zh, Fiz.Khim, 1974,48 (4), 810-12).But, the not record about using as catalyzer does not more have the record of result of use in this case in these documents.
Among the title complex that above-mentioned organic compound and boron trifluoride form, the title complex that known boron trifluoride and ethers form is preferably.When this boron trifluoride complex uses in various reactions, majority is to use boron trifluoride is organic solvent inert uses after boron trifluoride complex is diluted, and these inert organic solvents have aromatic hydrocarbon such as aliphatic hydrocarbon such as pentane, hexane, heptane, hexanaphthene and benzene, toluene.
Boron trifluoride complex solution can be used as polymerizing catalyst be used for trioxane homopolymerization or with the copolyreaction of cyclic ethers.Organic compound as forming title complex with boron trifluoride uses ethers such as diethyl ether, n-butyl ether usually.The title complex that forms can be organic solvent inert to boron trifluoride with hexane, heptane, hexanaphthene, benzene, toluene etc. and be diluted the back use.For example, at United States Patent (USP) the 2nd, 989, No. 510 and 2,989, put down in writing in No. 506 grades with the method for boron trifluoride n-butyl ether as the polymerizing catalyst use of trioxane; At United States Patent (USP) the 3rd, 027, put down in writing in No. 352 with the method for boron trifluoride diethyl etherate as the polymerisation catalysts use of trioxane and oxyethane.Recently,, disclose in No. 005 with equimolar boron trifluoride and n-butyl ether and formed boron trifluoride n-butyl ether title complex, then the polymerizing catalyst of the copolyreaction that encircles as trioxane and two oxa-s penta with hexanaphthene dilution back at United States Patent (USP) the 5th, 144.
Yet, existingly can form the boron trifluoride complex that the organic compound of title complex and boron trifluoride form with boron trifluoride, the title complex that forms of it and ethers particularly, when boron trifluoride being the mixed back of organic solvent inert dilution and using as the polymerisation catalysts of trioxane, the polyreaction performance is disorderly, fluctuation of service also has the problem of polymerization yield mutability simultaneously.In the past,, do not have effective solution, be difficult to keep stable polyreaction at above these problems.
The inventor etc. are for overcoming the above problems, through further investigation, found that, by making boron trifluoride and can reaching a certain specified proportion with its ratio (mol ratio) that forms the organic compound of title complex, the polyreaction operation stability is significantly improved, finished the present invention thus.
That is, the present invention relates to a kind of trioxane polymeric boron trifluoride complex solution that is used for, this solution is the boron trifluoride complex that is formed by (a) boron trifluoride and organic compound; And
(b) can form title complex with boron trifluoride but do not form the free organic compound of title complex;
The solution of forming that contains boron trifluoride complex, with respect to 1 mole of whole organic compound in this solution, the amount of corresponding boron trifluoride is below 0.98 mole.In addition, the invention still further relates to this solution that contains boron trifluoride complex of use as the polymerization of catalyzer De trioxane or the method for copolymerization.
Below, the present invention is described in detail.
In the solution that contains boron trifluoride of the present invention, when the total amount of amount and this organic compound that exists with free form that does not form title complex that forms the organic compound of title complex with boron trifluoride is 1 mole, the amount of corresponding boron trifluoride is below 0.98 mole, being the 0.98-0.01 mole preferably, better is 0.90 to 0.10 mole.When boron trifluoride surpasses 0.98 mole, can produce tarry precipitate, polyreaction operation stability variation in the polymerization of Zai trioxane and the copolyreaction.This ratio is provided with specific lower limit, if but measure very fewly, just need a large amount of organic compound, be difficult to find out that from the viewpoint of economy or device advantage is arranged.
Among the present invention, alcohols, ethers, organic acid, ester class etc. are arranged as organic compound with boron trifluoride formation title complex.Can use methyl alcohol, ethanol, propyl alcohol, acetic acid, diethyl ether, di-n-butyl ether etc. can form the organic compound of title complex particularly with boron trifluoride.In the present invention, particularly preferred organic compound is that the carbon number of each alkyl is 1 to 6 alkyl ether compound, as dme, di-n-propyl ether, di-n-butyl ether, amyl ether etc.Can use the mixture more than a kind or 2 kinds in these ether compounds.
Boron trifluoride complex solution of the present invention is used boron trifluoride is organic solvent inert dilution back use.As boron trifluoride being organic solvent inert aliphatic hydrocarbons such as pentane, hexane, heptane, octane, hexanaphthene are for example arranged; Aromatic hydrocarbon such as benzene, toluene.Preferred organic solvents has hexanaphthene, benzene, toluene.These organic solvents can directly use without pre-treatment, also can remove moisture or remove moisture by the adsorption dewatering operation of carrying out with zeolite etc. by distillation, do not have special restriction.Boron trifluoride is generally 0.01-30 weight % with the concentration of boron trifluoride complex after the inert organic solvents dilution, but has no particular limits.
The manufacture method of boron trifluoride complex solution of the present invention has no particular limits, for example, and can be by feeding boron trifluoride gas and obtain to forming in the organic compound such as ether, alcohol of title complex in accordance with regulations amount with boron trifluoride.Can be that equimolar boron trifluoride complex is further diluted with this organic compound and makes also with forming the organic compound of title complex and this boron trifluoride with boron trifluoride.
By the boron trifluoride complex solution of the present invention that above method obtains, can not add dilution directly as the polyreaction of catalyst action Yu trioxane, comparatively it is desirable to use boron trifluoride organic solvent inert dilution back is used.
Below further the polymerization of Dui trioxane be illustrated.
The polyreaction of trioxane, the homopolymerization of You trioxane and with the copolymerization of cyclic ethers.For example, trioxane and copolymerization can be adopted the self-cleaning reactor with monomeric copolyreaction, carry out polyreaction by block polymerization.As comonomer oxyethane, propylene oxide, 1 are arranged, 3-dioxolane, 1, cyclic ethers such as 4-butyleneglycol formal.With respect to trioxane, add 0.01-20mol% and carry out copolyreaction.Can also add methylal as molecular weight regulator.Polymerization temperature is 50 ℃-140 ℃, and the reaction times is 0.5 minute-60 minutes.In the polyreaction, when the amount that is used for forming the organic compound of title complex with boron trifluoride is 1 mole, the amount of corresponding boron trifluoride is below 0.98 mole, form boron trifluoride complex solution by the free organic compound and the boron trifluoride complex that do not form title complex with boron trifluoride, use then boron trifluoride is organic solvent inert dilution back uses as polymerizing catalyst.Usually, the concentration of polymerisation catalysts in boron trifluoride, with respect to 1 mole of whole polymerization single polymerization monomer, is 1 * 10
-6-1 * 10
-3Mole, but have no particular limits.
Below, the present invention is described further by embodiment, but the present invention is not subjected to any restriction of these embodiment.
Below, the evaluation to polymerization stability is described.
Polymerization stability: by following polymerization process, carry out trioxane and 1 continuously, the performance (the disorderly degree of operation) of its polyreaction is estimated in the copolyreaction of 3-dioxolane.
(polymerization process)
2 self-cleaning type reactor (L/D=8), being equipped with in its outside can be by the sleeve pipe of heat-transfer medium, inside is provided with homodromal two axles, the stirring rake of the convex lens shape of mutual interlock is housed on the axle, its long end parts and wall medial surface and be loaded between stirring rake on another and only keep very little space are keeping under the condition in so little space two axles being rotated.Reactor jacket remains on 80 ℃ of trioxanes with 2 kilograms/hour, 1, the 3-dioxolane is supplied with 1.2 Grams Per Hours continuously with 80 Grams Per Hours, methylal, simultaneously, with the mol ratio of boron trifluoride and organic compound is that the boron trifluoride complex solution of certain value is diluted to 1 weight % with hexanaphthene and adds reaction system than the back, carry out polymerization, keeping boron trifluoride concentration during polymerization is 1.2 * 10 with respect to 1 mole of trioxane
-5Mole.
(embodiment 1-6)
In ether compounds such as 1 mole of diethyl ether, di-n-butyl ether, mole number feeds boron triflouride gas in accordance with regulations, is modulated into boron trifluoride complex respectively.Use special grade chemical and utilize zeolite that the organic solvent that is used to dilute boron trifluoride complex is dewatered, moisture content is reached below the 10ppm, concoct afterwards.This blending liquid is carried out polyreaction as polymerisation catalysts by above-mentioned polymerization process.
As shown in Table 1, with respect to forming 1 mole of the organic compound of title complex with boron trifluoride, boron trifluoride be below 0.98 mole by the free organic compound that does not form title complex and boron trifluoride complex solution that boron trifluoride complex is formed when using as polymerisation catalysts, polymerization stability is good.
(comparative example 1-2)
Preparing boron trifluoride complex by the method identical, carry out polyreaction afterwards, estimate its polymerization stability with embodiment. the result is as shown in table 1.
As shown in Table 1, form the organic compound of title complex with respect to 1 mole of boron trifluoride complex or with boron trifluoride, boron trifluoride surpass 0.98 mole by the free organic compound that does not form title complex and boron trifluoride complex solution that boron trifluoride complex is formed when using as polymerisation catalysts, polymerization stability is poor.
Table 1
| Boron trifluoride is with respect to the mol ratio of organic compound | The kind of organic compound | The dilution inert organic solvents | Polymerization stability | ||
| The disorder of operation | The pollution of pipeline | ||||
| Embodiment 1 | ?????0.98 | Di-n-butyl ether | Hexanaphthene | Do not have in 2000 hours | Do not have |
| Embodiment 2 | ?????0.95 | The same | The same | The same | Do not have |
| Embodiment 3 | ?????0.75 | The same | The same | The same | Do not have |
| Embodiment 4 | ?????0.50 | The same | The same | The same | Do not have |
| Embodiment 5 | ?????0.25 | The same | Benzene | The same | Do not have |
| Embodiment 6 | ?????0.95 | Diethyl ether | Hexanaphthene | The same | Do not have |
| Comparative example 1 | ?????0.99 | Di-n-butyl ether | Hexanaphthene | Had later in 850 hours | Have a bit |
| Comparative example 2 | ?????1.00 | The same | Benzene | Had later in 700 hours | Have |
The present invention by use form by free organic compound that does not form title complex and boron trifluoride complex, wherein be that boron trifluoride complex solution below 0.98 mole uses as catalyzer with respect to 1 mole of this boron trifluoride of organic compound that forms title complex with boron trifluoride, realized the polymerization of Zai trioxane or the polymerization stability in the copolymerization first.
Utilize the present invention, eliminated the unstable of polyreaction performance disorder and operation, the polyreaction yield does not change and can realize continual and steady polymerization operation simultaneously.
Claims (6)
1. the boron trifluoride complex solution that is used for trioxane polymerization and copolyreaction, this solution are the boron trifluoride complexes that is formed by (a) boron trifluoride and organic compound; And
(b) can form title complex with boron trifluoride but do not form the free organic compound of title complex;
The solution of forming that contains boron trifluoride complex, with respect to 1 mole of whole organic compound in this solution, the amount of corresponding boron trifluoride is below 0.98 mole.
2. the boron trifluoride complex solution of claim 1 record, with respect to whole 1 mole of organic compound in the solution, the amount of boron trifluoride is the 0.98-0.01 mole.
Claim 1 or 2 the record the boron trifluoride complex solution, wherein organic compound is that the carbon number of alkyl is 1 to 6 alkylether compounds.
4. the boron trifluoride complex solution of each record in the claim 1,2 or 3, wherein the amount of boron trifluoride is the 0.90-0.10 mole.
5. the boron trifluoride complex solution of each record in the claim 1,2,3 or 4, wherein boron trifluoride complex solution is to use the solution that boron trifluoride is the organic solvent inert dilution.
6. the polymerization process of trioxane is characterized in that using the boron trifluoride complex solution of each record in the claim 1,2,3,4 or 5 to carry out the polymerization or the copolyreaction of trioxane or trioxane and cyclic ethers.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18185496 | 1996-07-11 | ||
| JP181854/96 | 1996-07-11 | ||
| JP181854/1996 | 1996-07-11 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1175596A true CN1175596A (en) | 1998-03-11 |
| CN1131254C CN1131254C (en) | 2003-12-17 |
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ID=16108000
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97114654A Expired - Lifetime CN1131254C (en) | 1996-07-11 | 1997-07-10 | Boron trifluoride complex for polymerization of trioxane |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN1131254C (en) |
| SG (1) | SG53008A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104558460A (en) * | 2013-10-22 | 2015-04-29 | 旭化成化学株式会社 | Manufacturing method of polyacetal copolymer |
| CN106905499A (en) * | 2015-10-28 | 2017-06-30 | 旭化成株式会社 | The manufacture method of Copolyacetal |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1005720B (en) * | 1985-11-27 | 1989-11-08 | 北京大学 | Method for producing polytetramethylene glycol |
| JPH0759615B2 (en) * | 1986-11-14 | 1995-06-28 | 三菱瓦斯化学株式会社 | Improved stabilization method for polyoxymethylene copolymers |
| JP2573406B2 (en) * | 1990-08-21 | 1997-01-22 | ポリプラスチックス株式会社 | Method for producing cyclic polyoxymethylene |
-
1997
- 1997-07-07 SG SG1997002393A patent/SG53008A1/en unknown
- 1997-07-10 CN CN97114654A patent/CN1131254C/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104558460A (en) * | 2013-10-22 | 2015-04-29 | 旭化成化学株式会社 | Manufacturing method of polyacetal copolymer |
| CN104558460B (en) * | 2013-10-22 | 2017-06-23 | 旭化成株式会社 | The manufacture method of Copolyacetal |
| CN106905499A (en) * | 2015-10-28 | 2017-06-30 | 旭化成株式会社 | The manufacture method of Copolyacetal |
| CN106905499B (en) * | 2015-10-28 | 2020-01-03 | 旭化成株式会社 | Method for producing polyacetal copolymer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1131254C (en) | 2003-12-17 |
| SG53008A1 (en) | 1998-09-28 |
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