CN101768078B - Itaconic acid derivant for copolymerization of acrylonitrile - Google Patents
Itaconic acid derivant for copolymerization of acrylonitrile Download PDFInfo
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- CN101768078B CN101768078B CN200810220710XA CN200810220710A CN101768078B CN 101768078 B CN101768078 B CN 101768078B CN 200810220710X A CN200810220710X A CN 200810220710XA CN 200810220710 A CN200810220710 A CN 200810220710A CN 101768078 B CN101768078 B CN 101768078B
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- itaconic acid
- acid derivant
- acrylonitrile
- methylene
- succinic acid
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Abstract
The invention discloses an itaconic acid derivant for copolymerization of acrylonitrile. The structural general formula (I) of the itaconic acid derivant is as follows: in the formula (I), R1 is alkyl. The itaconic acid derivant with both ester-base and ammonio is adopted as a comonomer for the acrylonitrile and the conventional ternary polymerization is replaced, so that the controllability of a copolymer is improved. The itaconic acid derivant is used for preparing high-performance PAN raw silks. In the copolymer of the acrylonitrile and the itaconic acid derivant, the mass ratio of the acrylonitrile is within 90 to 99.99%, and the mass ratio of the itaconic acid derivant is within 0.01 to 10%. The number-average molar mass of the copolymer is within 1 to 1 million.
Description
Technical field
The present invention relates to a kind of itaconic acid derivant.
Background technology
PAN-based carbon fiber has outstanding mechanical property, is the focus of thomel research in recent years.High-quality PAN precursor is the key of preparation high-performance PAN base carbon fibre, and synthetic high-quality acrylonitrile copolymer is the basis that obtains the high-quality polyacrylonitrile fibril.
The acrylonitrile homopolymer solvability is bad, and spinning property is relatively poor, and heat release is concentrated during preoxidation, is prone to cause the fiber defective.For improving spinning property and reducing the cyclisation temperature, adopt the method that adds other monomer copolymerizations to improve usually, common comonomer has methyl acrylate, TEB 3K, acrylic amide, methylene-succinic acid, vinylformic acid etc.The adding that it has been generally acknowledged that esters monomer can reduce spinning fluid viscosity, and can promote the transfer rate of oxygen in silk in the preoxidation process; Methylene-succinic acid class monomer then can reduce cyclisation activation energy, and cyclization process is carried out with ionic mechanism.Therefore, big quantity research all adopts esters of acrylic acid and methylene-succinic acid class monomer as comonomer simultaneously, the preparation terpolymer.
But the shortcoming of terpolymer is, because three pairs of monomeric 6 reactivity ratio parameters there are differences in the system, the multipolymer that obtains even segment distribution, good reproducibility is relatively more difficult.Comparatively speaking, the structure control of copolymer then wants simple a lot.For this reason, patent 200710056329.X has proposed to replace multiple single function monomer and acrylonitrile compolymer to obtain the thinking of high-performance PAN spinning solution with a kind of multifunctional monomer.
There is research to think that the reactivity ratio and the methylene-succinic acid of methylene-succinic acid ammonium are approaching, but higher wetting ability is arranged.Patent 02130021.6,02130023.2,02130024.0 provides a kind of and in homopolymer or copolymer, has fed ammonia; The indirect method that obtains terpolymer; Form equally distributed polymkeric substance though this in theory method can obtain segment, because polymers soln unusual heavy-gravity system normally, this gas liquid reaction is the heterogeneous reaction of a complicacy; The mass transfer difficulty, the homogeneity of polymer architecture can not get good assurance on the contrary.
Summary of the invention
The objective of the invention is to overcome the deficiency that prior art exists; A kind of itaconic acid derivant that is used for copolymerization of acrylonitrile is provided; The present invention adopts the itaconic acid derivant that has ester group and ammonium simultaneously as the acrylonitrile compolymer monomer; Replace conventional terpolymer, the controllability that multipolymer is formed is improved, and is used to prepare high-performance PAN precursor.
To achieve these goals, the present invention adopts following technical scheme:
A kind of itaconic acid derivant that is used for copolymerization of acrylonitrile, its general structure is suc as formula shown in (I):
In the formula (I), R
1Be alkyl.
In above-mentioned itaconic acid derivant, said R
1Be preferably a straight or aliphatic chain of 1～18 for the carbon atom number.Best carbon atom number is 1～6.
Below be the synthetic route of itaconic acid derivant of the present invention:
This method is to be raw material with the itaconic anhydride, at first prepares the methylene-succinic acid monoesters, with the reaction of excess of ammonia water, obtains title product then.Because the high reaction activity of itaconic anhydride, the reaction of acid anhydride and alcohol can be carried out waiting under the mol ratio.
This method is to be raw material with the methylene-succinic acid, with suitable excess fats alcohol reflux stoichiometric number hour, obtains β-methylene-succinic acid monoesters.The proper sourness catalyzer can further improve the yield of reaction.The reaction of methylene-succinic acid monoesters and excessive ammonia obtains then.
Compared with prior art; The present invention has following beneficial effect: the present invention adopts the itaconic acid derivant that has ester group and ammonium simultaneously as the acrylonitrile compolymer monomer; Replace conventional terpolymer, the controllability that multipolymer is formed is improved, and is used to prepare high-performance PAN precursor.In the multipolymer of vinyl cyanide and itaconic acid derivant, the mass ratio of vinyl cyanide is 90～99.99%; The mass ratio of itaconic acid derivant is 0.01～10%.The number-average molecular weight of multipolymer is 1～1,000,000.
Embodiment
Embodiment 1
0.1mol itaconic anhydride, 0.105mol ethanol are added in the 50ml Erlenmeyer flask, place 30 degree constant temperature shaking table reactions 24 hours, in bottle, add 15ml ammoniacal liquor then, concussion 30min.With product underpressure distillation 2 hours under 60 degree, obtain white solid and be itaconic acid derivant, yield 98%.
Embodiment 2
0.1mol methylene-succinic acid, 0.2mol methyl alcohol, 0.1ml concentrated hydrochloric acid are joined in the 50ml there-necked flask, and stirring reaction is 2 hours under 50 degree, drop reaction thing acid number to theoretical value, and excessive methanol and remaining hydrochloric acid are removed in decompression.Add 15ml ammoniacal liquor, concussion 30min.With product underpressure distillation 2 hours under 60 degree, obtain white solid and be itaconic acid derivant, yield 95%.
Embodiment 3
With 30g vinyl cyanide, 0.6g itaconic acid derivant (embodiment 1), 120g DMSO 99.8MIN. in the 250ml reaction flask; Constant temperature 50 degree behind the logical nitrogen 30min; Add the 0.15g ABVN, nitrogen protection was reacted 12 hours down, and the copolymer viscosity-average molecular weight that obtains is 160,000; MWD is 2.2, and monomer conversion is 91%.
Embodiment 4
ABVN among the embodiment 3 is changed to Diisopropyl azodicarboxylate, and temperature of reaction is 60 degree, and the polymericular weight that obtains is 120,000, and MWD is 2.6, and monomer conversion is 90%.
Claims (3)
1. itaconic acid derivant that is used for copolymerization of acrylonitrile, its general structure is suc as formula shown in (I):
In the formula (I), R
1It for the carbon atom number a straight or aliphatic chain of 1～6.
2. the preparation method of the said itaconic acid derivant of claim 1 is characterized in that comprising the steps:
(1) with the itaconic anhydride is raw material, preparation methylene-succinic acid monoesters;
(2) methylene-succinic acid monoesters and excess of ammonia water reaction obtains title product.
3. the preparation method of the said itaconic acid derivant of claim 1 is characterized in that comprising the steps:
(1) with the methylene-succinic acid is raw material,, obtains the methylene-succinic acid monoesters with the reaction of excess fats alcohol reflux;
(2) reaction of methylene-succinic acid monoesters and excessive ammonia obtains.
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| CN200810220710XA CN101768078B (en) | 2008-12-31 | 2008-12-31 | Itaconic acid derivant for copolymerization of acrylonitrile |
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| CN200810220710XA CN101768078B (en) | 2008-12-31 | 2008-12-31 | Itaconic acid derivant for copolymerization of acrylonitrile |
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| CN101768078A CN101768078A (en) | 2010-07-07 |
| CN101768078B true CN101768078B (en) | 2012-05-30 |
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Families Citing this family (3)
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| CN102747452A (en) * | 2011-04-20 | 2012-10-24 | 中国石油化工股份有限公司 | Preparation method of acrylonitrile copolymer spinning solution |
| CN103360251B (en) * | 2012-03-26 | 2015-03-18 | 中国科学院上海硅酸盐研究所 | Method for catalytically synthesizing mono-butyl itaconate at high selectivity |
| CN109553529B (en) * | 2018-12-03 | 2021-04-27 | 温州大学 | Acid-sensitive amphiphilic compound and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101158060A (en) * | 2007-11-20 | 2008-04-09 | 中国科学院长春应用化学研究所 | Binary acrylonitrile copolymer spinning fluid and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101158060A (en) * | 2007-11-20 | 2008-04-09 | 中国科学院长春应用化学研究所 | Binary acrylonitrile copolymer spinning fluid and preparation method thereof |
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