CN105622842B - Azacyclopropane and N- vinyl acetamides or the synthetic method with N- methyl-Nvinylacetamide copolymers - Google Patents
Azacyclopropane and N- vinyl acetamides or the synthetic method with N- methyl-Nvinylacetamide copolymers Download PDFInfo
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- CN105622842B CN105622842B CN201610165069.9A CN201610165069A CN105622842B CN 105622842 B CN105622842 B CN 105622842B CN 201610165069 A CN201610165069 A CN 201610165069A CN 105622842 B CN105622842 B CN 105622842B
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- methyl
- azacyclopropane
- vinyl
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
Abstract
A kind of synthetic method the invention discloses azacyclopropane and N vinyl acetamides or with N methyl N vinyl acetamide copolymers.Two azacyclopropane, N vinyl acetamides or N methyl Ns vinyl acetamide monomers are mixed, partial monosomy mixture and suitable quantity of water is taken to be added in reaction kettle, it opens and stirs and be passed through nitrogen, then heat to 60 65 DEG C, add in part initiator and part chain-transferring agent, heat release to be polymerized starts that residual monomer mixture is added dropwise later, its time for adding is 2 3h, after monomer mixture completion of dropwise addition, remaining initiator and chain-transferring agent are added in several times, reaction is terminated after polymer thermoviscosity reaches setting target, is cooled to 45 DEG C of dischargings.The polymer of preparation has the special performance of high charge density and high reaction activity, can further graft modification, can be widely applied to the fields such as coating, ink, adhesive, papermaking, sewage disposal, textile printing and dyeing and biological medicine.
Description
Technical field
The present invention relates to a kind of synthetic methods of cationic polymer, and in particular to a kind of azacyclopropane and N- vinyl second
Amide or the synthetic method with N- methyl-Nvinylacetamide copolymers.
Background technology
Azacyclopropane (CAS 151-56-4), N- vinyl acetamides (NVA) and N- methyl-Nvinylacetamides
(VMA) it is functional monomer, can its homopolymer or copolymer be obtained by different polymerizations.Such polymer sun from
Charge of the electron density is big, is widely used in the fields such as papermaking, water process, weaving, oil field, complexing of metal ion；It can also be used as
A kind of chemical products of many energy that have specific characteristics of starting material synthesis, such as pharmaceutical synthesis, dye transfer etc..NVA and VMA are mono-
Body has very high homopolymerization, and free radical polymerization is the such most convenient method of polymer of production, generally uses at present more
Azo initiators, such as two isobutyl imidazoline hydrochloride (AIBI) of azo and azo diisobutyl amidine hydrochloride (AIBA).It is theoretical
Upper most of inorganic peroxide initiators can cause the pH of reaction solution to decline when it is decomposed, and also having in the present invention can
It can cause the hydrolysis of NVA or VMA monomers, but its dosage is seldom, and also it is cheap and easy to get, so part inorganic peroxide initiator
Application in the present invention is also a good selection.
Azacyclopropane (12 DEG C of flash-point), N- vinyl acetamides (NVA) (108 DEG C of flash-point) and N- methyl-N-vinyl second
Amide (VMA) (58 DEG C of flash-point), since these three functional monomer stability are poor, manufacturing process is complicated, at present by only a few
External producer is directly produced into polymer and is sold, and the domestic industrialized production research to above-mentioned monomer and such polymer is all
Seldom.
The content of the invention
It is an object of the invention to provide a kind of azacyclopropane and N- vinyl acetamides or with N- methyl-N-vinyl second
The synthetic method of amide copolymer, the high charge density and high reaction activity of such polymer, application field is extensive, is conducive to push away
It moves the product up-gradation of its application field and improves its value-added content of product.
To achieve the above object of the invention, the step of the technical solution adopted by the present invention is as follows：
(1) dispensing, following components is by weight percentage：
Azacyclopropane 5-80%, N- vinyl acetamide or N- methyl-Nvinylacetamide 5-80%, water solubility trigger
Agent 0.2-3.0%, chain-transferring agent 0.1-3.0%, deionized water 10-80%；
(2) polymerisation in solution：Azacyclopropane and N- vinyl acetamides or N- methyl-Nvinylacetamides are mixed, taken
The mixture of 5-85% is made an addition in reaction kettle, is opened and is stirred and be passed through nitrogen, remaining monomer mixture is positioned over a drop
Add in slot；The deionized water of 5-90% is directly added in reaction kettle, and material in kettle is heated to 60-65 DEG C；By 5-20%
Initiator and the chain-transferring agent of 5-20% be added to simultaneously in reaction kettle, treat that material polymerization exotherm is opened after 70-80 DEG C in kettle
Begin to be added dropwise remaining monomer mixture, time for adding 2-3h, add in several times after monomer dropping remaining initiator and
Chain-transferring agent terminates reaction, after adding remaining deionized water after the thermoviscosity of material in kettle reaches 2000cps~8000cps
It is cooled to 45 DEG C of dischargings.
The water soluble starter is hydrogen peroxide, ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, two NSC 18620 salt of azo
Hydrochlorate, two isobutyl imidazoline hydrochloride of azo, azo dicyano valeric acid, two N- hydroxyisobutyl amidines hydrate of azo, azo two
In isopropylimdazole quinoline, azo two N, N ' cyclobutyl isobutyl amidine hydrate, azo dimethyl N-2- hydroxyl butylacrylamides
It is a kind of.
The chain-transferring agent is isopropanol, thioacetic acid, mercaptoethanol, sodium sulfite, sodium hypophosphite, sodium formate, first
One kind or two kinds arbitrary in base Sodium Allyl Sulfonate, Sodium Allyl Sulfonate.
Compared with background technology, the invention has the advantages that：
1) cationic polymer of synthesis, it has high charge density and high reaction activity simultaneously.
2) in the polymer molecule the very unique performance of polymer is imparted containing groups such as primary amine, secondary amine, tertiary amines.
3) polymer can be used directly as product, can also be on the groups such as primary amine, secondary amine, by further connecing
The other active groups of branch, are modified, can obtain more excellent performance of derivative.
The polymer and its derivative of the present invention can be widely applied to coating, ink, adhesive, papermaking, sewage disposal, spinning
Knit the fields such as printing and dyeing and biological medicine.
Specific embodiment
With reference to embodiment, the present invention is further illustrated (following components is by weight percentage), but this hair
Bright embodiment is without being limited thereto.
Embodiment 1：
It weighs 15 grams of azacyclopropanes, 5 grams of N- vinyl acetamides and 90 grams of deionized waters to add in reaction kettle, opens stirring
And nitrogen is passed through, it starts to warm up to 63 DEG C, adding in initiator azo-bis-isobutyrate hydrochloride (V50) aqueous solution 5g, (concentration is
2.0%) with chain-transferring agent methallylsulfonic acid sodium water solution 5g (concentration 2.0%), material in reactor polymerization exotherm is treated
Temperature stabilization starts that 135 grams of azacyclopropanes and 45 grams of N- vinyl acetamides, monomer mixture time for adding is added dropwise after 75 DEG C
For 2.5h, point 3 equivalent add in V50 initiator solutions each 15g, interval time 30min after completion of dropwise addition, add in for the first time
Methallylsulfonic acid sodium water solution 10g need to be added in during initiator simultaneously, when the thermoviscosity of reaction kettle interpolymer reaches
During 5000cps, sodium sulfite aqueous solution 20g (concentration 2.0%) and 25g water are added in immediately, are cooled to 45 DEG C and are obtained sample 1#.
Embodiment 2：
It weighs in 70 grams of azacyclopropanes, 10 grams of N- methyl-Nvinylacetamides addition reaction kettles, opens stirring and be simultaneously passed through
Nitrogen is started to warm up to 60 DEG C, adds in initiator potassium persulfate aqueous solution 5g (concentration 2.0%) and chain-transferring agent sodium sulfite
Aqueous solution 10g (concentration 2.0%) treats that material in reactor polymerization exotherm temperature stabilization starts that 210 grams of rings are added dropwise after 80 DEG C
Ethyleneimine and 30 grams of N- methyl-Nvinylacetamides, monomer mixture time for adding are 3h, point 3 equivalent after completion of dropwise addition
Persulfate aqueous solution each 15g, interval time 30min are added in, when the thermoviscosity of reaction kettle interpolymer reaches 8000cps
When, sodium sulfite aqueous solution 20g (concentration 2.0%) is added in immediately, is cooled to 45 DEG C and is obtained sample 2#.
Embodiment 3：
It weighs 10 grams of azacyclopropanes, 10 grams of N- vinyl acetamides and 150 grams of deionized waters to add in reaction kettle, unlatching is stirred
It mixes and is passed through nitrogen, start to warm up to 65 DEG C, add in two isobutyl imidazoline hydrochloride (VA-044) aqueous solution 5g of initiator azo
(concentration 2.0%) and chain-transferring agent aqueous sodium formate solution 5g (concentration 2.0%), treats material in reactor polymerization exotherm temperature
To stablize and start that 30 grams of azacyclopropanes and 30 grams of N- vinyl acetamides are added dropwise after 70 DEG C, monomer mixture time for adding is 2h,
Point 3 equivalent add in VA-044 initiator solutions each 15g, interval time 30min after completion of dropwise addition, add in trigger for the first time
Aqueous sodium formate solution 5g (concentration 2.0%) need to be added in during agent simultaneously, when the thermoviscosity of reaction kettle interpolymer reaches 2000cps
When, chain-transferring agent ortho phosphorous acid sodium water solution 20g (concentration 2.0%) and 95g water are added in immediately, are cooled to 45 DEG C and are obtained sample
3#。
Since such polymer specification is relatively more, range of solid content from 10% to 90% more than, finished product viscosity is from 500cps
To more than 100000cps, therefore above-described embodiment is only given the technical characteristic of claim and is described in detail, to support right will
It asks, it, can not be with its object is to allow the professional for being familiar with technique that can understand present disclosure and implement according to this
This is limited the scope of the invention.Any equivalent change or modification in accordance with the spirit of the invention should all cover at this
Within the protection domain of invention.
Test analysis and evaluation
1. amine value is analyzed
Amine value is one of characteristic index of such polymer, need to be detected using anhydrous system acidimetry.Amine value
Higher, the alkalescence of polymer is stronger.
1 amine value test data of table
2. decomposition temperature
It is detected in nitrogen using differential scanning calorimetry, is conducive to determine the thermal stability of polymer.Table 2 decomposes
Temperature
Claims (3)
1. a kind of azacyclopropane and N- vinyl acetamides or the synthetic method with N- methyl-Nvinylacetamide copolymers,
It is characterized in that：The step of this method, is as follows：
（1）Dispensing, following components is by weight percentage：
Azacyclopropane 5-80%, N- vinyl acetamide or N- methyl-Nvinylacetamide 5-80%, water soluble starter
0.2-3.0%, chain-transferring agent 0.1-3.0%, deionized water 10-80%；
（2）Polymerisation in solution：Azacyclopropane and N- vinyl acetamides or N- methyl-Nvinylacetamides are mixed, take 5-85%
Mixture make an addition in reaction kettle, open stir simultaneously be passed through nitrogen, remaining monomer mixture is positioned in a dropwise adding tank；
The deionized water of 5-90% is directly added in reaction kettle, and material in kettle is heated to 60-65 DEG C；By the initiator of 5-20% and
The chain-transferring agent of 5-20% is added in reaction kettle simultaneously, treats that material polymerization exotherm starts to be added dropwise remaining after 70-80 DEG C in kettle
Monomer mixture, time for adding 2-3h add in remaining initiator and chain-transferring agent after monomer dropping, work as kettle several times
The thermoviscosity of interior material reaches 2000cps ~ 8000cps and terminates reaction, and 45 DEG C of dischargings are cooled to after adding remaining deionized water.
2. a kind of azacyclopropane according to claim 1 and N- vinyl acetamides or with N- methyl-N-vinyl acetyl
The synthetic method of amine copolymer object, it is characterised in that：The water soluble starter is hydrogen peroxide, ammonium persulfate, potassium peroxydisulfate, mistake
Sodium sulphate, azo-bis-isobutyrate hydrochloride, two isobutyl imidazoline hydrochloride of azo, azo dicyano valeric acid, two N- hydroxyls of azo
Isobutyl amidine hydrate, azo dicyclohexyl formonitrile HCN, azo two N, N ' cyclobutyl isobutyl amidine hydrate, azo dimethyl N-
One kind in 2- hydroxyl butylacrylamides.
3. a kind of azacyclopropane according to claim 1 and N- vinyl acetamides or with N- methyl-N-vinyl acetyl
The synthetic method of amine copolymer object, it is characterised in that：The chain-transferring agent is isopropanol, thioacetic acid, mercaptoethanol, sulfurous acid
Sodium, sodium hypophosphite, sodium formate, methallylsulfonic acid sodium, one kind in Sodium Allyl Sulfonate or two kinds arbitrary.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610165069.9A CN105622842B (en) | 2016-03-22 | 2016-03-22 | Azacyclopropane and N- vinyl acetamides or the synthetic method with N- methyl-Nvinylacetamide copolymers |
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| CN201610165069.9A CN105622842B (en) | 2016-03-22 | 2016-03-22 | Azacyclopropane and N- vinyl acetamides or the synthetic method with N- methyl-Nvinylacetamide copolymers |
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| CN105622842A CN105622842A (en) | 2016-06-01 |
| CN105622842B true CN105622842B (en) | 2018-05-22 |
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| CN201610165069.9A Expired - Fee Related CN105622842B (en) | 2016-03-22 | 2016-03-22 | Azacyclopropane and N- vinyl acetamides or the synthetic method with N- methyl-Nvinylacetamide copolymers |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3306881A (en) * | 1963-06-06 | 1967-02-28 | Gen Aniline & Film Corp | Method of making insoluble polymers of n-vinyl imides |
| US6150477A (en) * | 1996-06-24 | 2000-11-21 | Hoechst Aktiengesellschaft | Process for the preparation of hydrophilic hydrogels of high swelling capacity |
| CN102304200A (en) * | 2011-05-27 | 2012-01-04 | 中国海洋石油总公司 | Crosslinked polymer microspheres and preparation method thereof |
-
2016
- 2016-03-22 CN CN201610165069.9A patent/CN105622842B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3306881A (en) * | 1963-06-06 | 1967-02-28 | Gen Aniline & Film Corp | Method of making insoluble polymers of n-vinyl imides |
| US6150477A (en) * | 1996-06-24 | 2000-11-21 | Hoechst Aktiengesellschaft | Process for the preparation of hydrophilic hydrogels of high swelling capacity |
| CN102304200A (en) * | 2011-05-27 | 2012-01-04 | 中国海洋石油总公司 | Crosslinked polymer microspheres and preparation method thereof |
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Effective date of registration: 20201110 Address after: 201512 No.389, Jinou Road, the second industrial zone, Jinshanwei Town, Jinshan District, Shanghai Patentee after: QUNLI CHEMICAL Co.,Ltd. SHANGHAI Address before: 310018, No. 928, No. 2, Poplar Street, Jianggan Economic Development Zone, Hangzhou, Zhejiang Patentee before: ZHEJIANG SCI-TECH University |
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