CN108456299B - A method of improving the interior hydroxyl reactivity of isobide - Google Patents
A method of improving the interior hydroxyl reactivity of isobide Download PDFInfo
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- CN108456299B CN108456299B CN201810033666.5A CN201810033666A CN108456299B CN 108456299 B CN108456299 B CN 108456299B CN 201810033666 A CN201810033666 A CN 201810033666A CN 108456299 B CN108456299 B CN 108456299B
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- 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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
- C08G64/305—General preparatory processes using carbonates and alcohols
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Abstract
本发明涉及一种提高异山梨醇的内羟基反应活性的方法(异山梨醇与碳酸酯进行酯交换反应时)。所述方法的主要步骤是，由异山梨醇和碳酸酯，在180℃～220℃及有催化剂存在条件下，经熔融酯交换反应，得到目标物，所得目标物中，外羟基与内羟基的含量比值大于1。其中，所述催化剂是：含与羰基的配位能力常数(lgβ1)大于6的金属离子的化合物。
The present invention relates to a method for improving the reaction activity of the internal hydroxyl group of isosorbide (when isosorbide and carbonate undergo transesterification). The main steps of the method are as follows: from isosorbide and carbonate, under the condition of 180 ℃～220 ℃ and the presence of a catalyst, through a melt transesterification reaction, the target substance is obtained, and the content of the outer hydroxyl group and the inner hydroxyl group in the obtained target substance is The ratio is greater than 1. Wherein, the catalyst is a compound containing a metal ion whose coordination ability constant (lgβ1) with a carbonyl group is greater than 6.
Description
Technical field
The present invention relates to a kind of methods of interior hydroxyl (endo-OH) reactivity for improving isobide.Specifically, relating to
A kind of and method for improving isobide endo-OH reactivity (when isobide and carbonic ester carry out ester exchange reaction).
Background technique
The polycarbonate prepared using isobide as monomer optical transparence, mechanical strength and in terms of can
The polycarbonate to match in excellence or beauty by bisphenol-A for monomer preparation, and started to completely forbid at present and exist by the polycarbonate of monomer of bisphenol-A
Use in infant's container (such as feeding bottle), container for food.Therefore, isobide polycarbonate substitution bisphenol-a polycarbonate tool
There is powerful application background.Isobide and carbonic ester melting state transesterification reaction are the passes that " melt-polycondensation " prepares polycarbonate
Key step.In general, which determine the performance of prepared polycarbonate (such as height of glass transition temperature (Tg) and made
The size of the molecular weight of standby polycarbonate).
Isobide belongs to secondary alcohol, and acidity is low (with bisphenol-A ratio), the activity with the melting state transesterification reaction of carbonic ester
It is low.In addition, having interior hydroxyl (endo-OH) and outer hydroxyl (exo-OH) two kinds of hydroxyl in the molecular structure of isobide
Base, wherein there are hydrogen bond actions between endo-OH and ortho position oxygen heterocycle, and steric hindrance is big, lead to the reactivity of endo-OH
Lower (as shown in formula A).
In order to improve the reactivity of isobide hydroxyl, many researchers (are prepared for high activity group substituted hydroxy
A series of isosorbide derivatives), using isosorbide derivatives as raw material, prepare isobide type polycarbonate.But this side
Method will first carry out in advance the reaction such as carboxylic acid halides (such as chloride) or benzene methyl to isobide, then carry out subsequent reactions and (melt
Melt ester exchange reaction and melt polycondensation reaction) prepare isobide type polycarbonate.In this way, not only increasing reaction step (shadow
Ring yield), and the risk of pollution environment is increased, it is unable to satisfy the demand for development of social low-carbon environment-friendly now.
Therefore, how it is succinct improve efficiently and safely, in the melting state transesterification reaction of isobide and carbonic ester, different mountain
The reactivity (the especially reactivity of the endo-OH of isobide) of pears alcohol, is the technical problem to be solved in the invention.
Summary of the invention
The present inventor it has been investigated that: isobide and some specific carbonic esters carry out melting state transesterification reactions
When, it is only necessary to a little specific metallic compounds are added, reactivity (the especially endo- of isobide of isobide can be improved
The reactivity of OH).
Therefore, the object of the present invention is to provide a kind of isobide (compounds shown in Formulas I) and carbonic ester (Formula II institute
Show compound) melting state transesterification reaction when, improve Formulas I shown in compound interior hydroxyl (endo-OH) reactivity method.
The method has main steps that, compound shown in compound and Formula II as shown in Formulas I, at 180 DEG C~220 DEG C and
Have under catalyst existence condition, through melting state transesterification reaction, obtain object, in gained object, outer hydroxyl (exo-OH) with
The content ratio of interior hydroxyl (endo-OH) is greater than 1；
Wherein, the catalyst is: the chemical combination of the metal ion containing the coordination ability constant (lg β 1) with carbonyl greater than 6
Object, R1And R2It is respectively and independently selected from: C1~C6The alkyl of linear chain or branched chain, phenyl or the substituent group with electron effect replace
Phenyl in it is a kind of.
Above-mentioned technical proposal (present invention) has the following characteristics that
(1) it is catalyst due to using specific metallic compound in the melting state transesterification reaction, improves different mountain
The interior hydroxyl (endo-OH) of pears alcohol reactivity (in the object of melting state transesterification reaction, outer hydroxyl (exo-OH) and interior hydroxyl
The content ratio of base (endo-OH) is greater than 1)；
(2) since the reactivity of the interior hydroxyl (endo-OH) of isobide is improved, so that (molten in end-products
The object for melting ester exchange reaction obtains after polycondensation, detailed in Example) Chinese style a1Shown in structure fragment content increase, from
And the performance (such as Tg and molecular weight) of the end-products can be improved；
(3) compared with the prior art (its derivative (such as acetyl derivatives or chloride derivative first is made in isobide
Deng), then with carbonic ester (compound shown in Formula II) carry out melting state transesterification reaction) for, step of the invention is more succinct.
Detailed description of the invention
Fig. 1 is the typical nucleus magnetic hydrogen spectrum of melting state transesterification reaction product (sodium hydroxide is catalysis preparation)；
Fig. 2 is the typical nuclear-magnetism carbon spectrum of polycarbonate (sodium hydroxide is catalysis preparation).
Specific embodiment
The coordination ability constant (lg β 1) of metal ion described previously, referring specifically to document Polymer, 1975,16,185-
190。
In a preferred technical solution of the invention, the catalyst is: containing coordination ability constant (the lg β with carbonyl
1) compound of the metal ion more than or equal to 7；
Preferred technical solution is: the catalyst is selected from: (containing two kinds) one or more kinds of in following compounds
Mixture:
Zinc oxide, zinc chloride, zinc nitrate, zinc sulfate, zinc sulfite, zinc carbonate, bicarbonate zinc, zinc fluoride, zinc bromide, iodine
Change the compounds containing divalent zinc such as zinc, zinc acetate, zinc acetylacetonate, zinc oxalate, trbasic zinc phosphate,
Calcium oxide, calcium chloride, calcium nitrate, calcium sulfate, calcium sulfite, calcium carbonate, calcium bicarbonate, calcirm-fluoride, calcium bromide, iodine
Change the compounds containing divalent calcium such as calcium, calcium acetate, zinc oxalate, calcium acetylacetonate, calcium phosphate,
Barium monoxide, barium chloride, barium nitrate, barium sulfate, barium sulfite, barium carbonate, barium bicarbonate, barium fluoride, barium bromide, iodine
Change the compound of the barium containing divalent such as barium, barium acetate, barium oxalate, acetylacetone barium, barium phosphate,
Magnesia, magnesium chloride, magnesium nitrate, magnesium sulfate, magnesium sulfite, magnesium carbonate, magnesium bicarbonate, magnesium fluoride, magnesium bromide, iodine
Change the compounds containing divalent magnesium such as magnesium, magnesium acetate, magnesium oxalate, magnesium acetylacetonate, magnesium phosphate,
Copper oxide, copper chloride, copper nitrate, copper sulphate, sulfurous acid copper, copper carbonate, bicarbonate copper, copper fluoride, copper bromide, iodine
Change copper, copper acetate, cupric oxalate, acetylacetone copper, cupric phosphate etc. and contains cupric compound, or,
Strontium oxide strontia, strontium chloride, strontium nitrate, strontium sulfate, strontium sulfite, strontium carbonate, strontium bicarbonate, strontium fluoride, strontium bromide, iodine
Change the compound of the strontiums containing divalent such as strontium, strontium acetate, strontium oxalate, acetylacetone,2,4-pentanedione strontium, strontium phosphate.
Further technical solution is: the catalyst is selected from: one or more kinds of in following compounds (containing two
Kind) mixture:
Calcium chloride, zinc acetate, zinc oxide, zinc chloride or calcium phosphate.
In presently preferred technical solution, R1And R2It is respectively and independently selected from: in phenyl or substituent group substituted-phenyl
One kind,
The substituent group of the substituted-phenyl is selected from: (containing two kinds) one or more kinds of in following groups:
C1~C4The alkyl of linear chain or branched chain, C1~C4The alkoxy of linear chain or branched chain, hydroxyl (OH) or amino (NH2), it takes
The number of Dai Ji is 1~5.
Preferred technical solution is: R1And R2It is phenyl.
In another optimal technical scheme of the invention, isobide (compound shown in Formulas I) and carbonic ester are (shown in Formula II
Compound) molar ratio be 1.00:(1.00~1.50), the concentration of catalyst in the reaction system be 1~104ppm。
The present invention is further elaborated below by embodiment, purpose, which is only that, is best understood from the contents of the present invention.
Therefore, the cited case of the present invention does not limit the scope of the invention.
Embodiment 1
By 0.10mol isobide, 0.15mol diphenyl carbonate and 104Ppm zinc chloride is added in 500mL three-necked flask,
It is warming up to 180 DEG C, constant temperature 30 minutes；220 DEG C are warming up to, constant temperature 20 minutes, obtains transesterification product A.
Terminal hydroxy group in transesterification product A is contained using Nuclear Magnetic Resonance (Bruker DMX-400NMR spectrometer)
Amount is tested and analyzed.Transesterification product A is dissolved in deuterated chloroform, concentration 40g/L, using TMS as internal standard.Nucleus magnetic hydrogen spectrum
In, be normalized with the integral area of No. 3 proton peaks of repetitive unit (see Fig. 1), calculate outer hydroxyl (exo-OH) with it is interior
The content ratio of hydroxyl (endo-OH), concrete outcome are shown in Table 1.
Gained transesterification product A is continuously heating to 230 DEG C, increase vacuum degree to 40Torr is continuously heating to 250 DEG C,
Increase vacuum degree to 2Torr is lower than, constant temperature 20 minutes, obtains polycondensation crude product.Polycondensation crude product precipitates after being dissolved in methylene chloride
In methanol, and it is vacuum dried obtain purification polycondensation product A.
Using Nuclear Magnetic Resonance (Bruker DMX-400NMR spectrometer) to purification polycondensation product A Chinese style a1Institute
The structure fragment shown is tested and analyzed.Polycondensation product A will be refined to be dissolved in deuterated chloroform, concentration 40g/L is with TMS
Internal standard.In nuclear-magnetism carbon spectrum, with formula a2Shown in the carbon peak integral area of structure fragment be normalized (see Fig. 2), calculate
a1、a2And a3The content of structure fragment, concrete outcome are shown in Table 1.
Embodiment 2
Outside divided by zinc chloride in zinc oxide alternative embodiment 1, other conditions and step are same as Example 1, can obtain respectively
To transesterification product B and purification polycondensation product B.Using exo- in test method test transesterification product B same as Example 1
The content ratio of OH and endo-OH, and purification polycondensation product B Chinese style a1Shown in structure fragment content.Concrete outcome is shown in Table
1。
Embodiment 3
Outside divided by zinc chloride in calcium carbonate alternative embodiment 1, other conditions and step are same as Example 1, can obtain respectively
To transesterification product C and purification polycondensation product C.Using exo- in test method test transesterification product C same as Example 1
The content ratio of OH and endo-OH, and purification polycondensation product C Chinese style a1Shown in structure fragment content.Concrete outcome is shown in Table
1。
Embodiment 4
Outside divided by zinc chloride in calcium chloride alternative embodiment 1, other conditions and step are same as Example 1, can obtain respectively
To transesterification product D and purification polycondensation product D.Using exo- in test method test transesterification product D same as Example 1
The content ratio of OH and endo-OH, and purification polycondensation product D Chinese style a1Shown in structure fragment content.Concrete outcome is shown in Table
1。
Embodiment 5
Outside divided by zinc chloride in zinc acetate alternative embodiment 1, other conditions and step are same as Example 1, can obtain respectively
To transesterification product E and purification polycondensation product E.Using exo- in test method test transesterification product E same as Example 1
The content ratio of OH and endo-OH, and purification polycondensation product E Chinese style a1Shown in structure fragment content.Concrete outcome is shown in Table
1。
Comparative example 1
Outside divided by zinc chloride in sodium hydroxide alternative embodiment 1, other conditions and step are same as Example 1, can distinguish
Obtain transesterification product a and purification polycondensation product a.Using in test method test transesterification product a same as Example 1
The content ratio of exo-OH and endo-OH, and purification polycondensation product a Chinese style a1Shown in structure fragment content.Concrete outcome
It is shown in Table 1.
Comparative example 2
Outside divided by zinc chloride in sodium bicarbonate alternative embodiment 1, other conditions and step are same as Example 1, can distinguish
Obtain transesterification product b and purification polycondensation product b.Using in test method test transesterification product b same as Example 1
The content ratio of exo-OH and endo-OH, and purification polycondensation product b Chinese style a1Shown in structure fragment content.Concrete outcome
It is shown in Table 1.
Comparative example 3
Outside divided by zinc chloride in sodium methoxide alternative embodiment 1, other conditions and step are same as Example 1, can obtain respectively
To transesterification product c and purification polycondensation product c.Using exo- in test method test transesterification product c same as Example 1
The content ratio of OH and endo-OH, and purification polycondensation product c Chinese style a1Shown in structure fragment content.Concrete outcome is shown in Table
1。
Comparative example 4
Outside divided by zinc chloride in cesium carbonate alternative embodiment 1, other conditions and step are same as Example 1, can obtain respectively
To transesterification product d and purification polycondensation product d.Using exo- in test method test transesterification product d same as Example 1
The content ratio of OH and endo-OH, and purification polycondensation product d Chinese style a1Shown in structure fragment content.Concrete outcome is shown in Table
1。
Comparative example 5
Outside divided by zinc chloride in sodium acetate alternative embodiment 1, other conditions and step are same as Example 1, can obtain respectively
To transesterification product e and purification polycondensation product e.Using exo- in test method test transesterification product e same as Example 1
The content ratio of OH and endo-OH, and purification polycondensation product e Chinese style a1Shown in structure fragment content.Concrete outcome is shown in Table
1。
Table 1
* intrinsic viscosity: purification polycondensation product being dissolved in chloroform, concentration 10g/L is made, temperature 25 ±
Under the conditions of 0.5 DEG C, using determination of ubbelohde viscometer and acquisition is calculated.
Claims (7)
1. a kind of isobide and carbonic ester melting state transesterification reaction are provided, the reactivity of the interior hydroxyl of isobide is improved
Method,
The method has main steps that compound shown in compound and Formula II as shown in Formulas I at 180 DEG C~220 DEG C and is urged
Under agent existence condition, through melting state transesterification reaction, object is obtained, in gained object, the content of outer hydroxyl and interior hydroxyl
Ratio is greater than 1；
Wherein, the catalyst is: the compound containing the metal ion with the coordination ability constant of carbonyl greater than 6, R1And R2Respectively
It is independently selected from: C1~C6It is a kind of in the phenyl that the alkyl of linear chain or branched chain, phenyl or the substituent group with electron effect replace.
2. the method as described in claim 1, which is characterized in that wherein the catalyst is: containing normal with the coordination ability of carbonyl
The compound of metal ion of the number more than or equal to 7.
3. method according to claim 2, which is characterized in that wherein the catalyst is: calcium chloride, zinc acetate, zinc oxide,
Zinc chloride or/and calcium phosphate.
4. the method as described in claim 1, which is characterized in that wherein R1And R2Be respectively and independently selected from: phenyl or substituent group replace
It is a kind of in phenyl；The substituent group of the substituted-phenyl is selected from: one or more kinds of in following groups:
C1~C4The alkyl of linear chain or branched chain, C1~C4The alkoxy of linear chain or branched chain, hydroxyl or amino, the number of substituent group are 1
~5.
5. method as claimed in claim 4, which is characterized in that wherein R1And R2It is phenyl.
6. the method as described in any one of Claims 1 to 5, which is characterized in that wherein used catalyst is in reaction system
In concentration be 1ppm~104ppm。
7. the method as described in any one of Claims 1 to 5, which is characterized in that wherein compound shown in Formulas I and Formula II institute
The molar ratio for showing compound is 1.00:(1.00~1.50).
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101889041A (en) * | 2007-10-18 | 2010-11-17 | 沙伯基础创新塑料知识产权有限公司 | Isosorbide-based polycarbonates, method of making, and articles formed therefrom |
| CN103204987A (en) * | 2012-01-17 | 2013-07-17 | 常州化学研究所 | Method for synthesizing high-molecular-weight aliphatic polycarbonate |
| CN106256845A (en) * | 2015-06-19 | 2016-12-28 | 中国科学院成都有机化学有限公司 | A kind of preparation method of high-molecular aliphatic polycarbonate |
| CN106800643A (en) * | 2017-02-09 | 2017-06-06 | 中国科学院化学研究所 | A kind of preparation method of high-fire resistance isobide type atactic polyester |
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- 2018-01-12 CN CN201810033666.5A patent/CN108456299B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101889041A (en) * | 2007-10-18 | 2010-11-17 | 沙伯基础创新塑料知识产权有限公司 | Isosorbide-based polycarbonates, method of making, and articles formed therefrom |
| CN103204987A (en) * | 2012-01-17 | 2013-07-17 | 常州化学研究所 | Method for synthesizing high-molecular-weight aliphatic polycarbonate |
| CN106256845A (en) * | 2015-06-19 | 2016-12-28 | 中国科学院成都有机化学有限公司 | A kind of preparation method of high-molecular aliphatic polycarbonate |
| CN106800643A (en) * | 2017-02-09 | 2017-06-06 | 中国科学院化学研究所 | A kind of preparation method of high-fire resistance isobide type atactic polyester |
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