CN1486997A - Nitrogenous polymer containing long-chain allyl ester and maleic anhydride monomer and its prepn - Google Patents
Nitrogenous polymer containing long-chain allyl ester and maleic anhydride monomer and its prepn Download PDFInfo
- Publication number
- CN1486997A CN1486997A CNA031418295A CN03141829A CN1486997A CN 1486997 A CN1486997 A CN 1486997A CN A031418295 A CNA031418295 A CN A031418295A CN 03141829 A CN03141829 A CN 03141829A CN 1486997 A CN1486997 A CN 1486997A
- Authority
- CN
- China
- Prior art keywords
- maleic anhydride
- monomer
- multipolymer
- nitrogen
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The nitrogenous polymer preparing process includes the following steps: copolymeriaztion of maleic anhydride monomer and vinyl group containing monomer to obtain copolymer; and amination or imidation of the copolymer in solvent of organic amine to obtain the nitrogenous copolymer. The polymer of the present invention may be used as functional modifying assistant, which is blended with polypropylene and spin to improve the acid dyeability of polypropylene fiber. The polymer of the present invention has higher polar group content and high polypropylene compatibility, so that it may be blended simply with polypropylene.
Description
Technical field
The present invention relates to a kind of polymer with nitrogen that contains allyl group long-chain ester and maleic anhydride monomer and preparation method thereof, particularly a kind of polymkeric substance that is used to improve polypropylene fibre dyeability energy.
Background technology
The acid dyeable modification of polypropylene fibre is a difficult problem that solves fully not yet so far, and for this reason, numerous scientific and technical personnel have done number of research projects.Improve in the whole bag of tricks of dyeing polypropylene fibers performance, blending method is to realize the most feasible method of industrial application, also is the more direction of correlative study.Select which kind of multipolymer and polypropene blended, determined the blending and modifying fiber also can be made polypropylene and the stronger polymer blending of another kind of polarity by the performance of which kind of dyeing and fiber as compatilizer.
J.Akrman and colleague thereof have done a lot of exploration work in the research of acid dyeable polypropylene fibre, their used blend additive is the derivative (using 3-dimethylamino propylamine, stearylamine and morpholinyl propylamine to the MALEIC ANHYDRIDE imidization) of MALEIC ANHYDRIDE-cinnamic multipolymer, melt-spinning has obtained the acid dyeable polypropylene fibre after the blend, has obtained effect preferably.
Document " Dyeing polypropylene fibers by means of copolymer additives " (J.S.D.C., 1994,110:19-23) disclosed three kinds of multipolymers, be by the methacrylic acid stearyl respectively with (a) MALEIC ANHYDRIDE; (b) N replaces ((dimethylamino) propyl group) acrylamide; (c) three kinds of material copolymerization of toxilic acid hydrazides, independent or mixing and polypropene blended and melt-spinning with these three kinds of multipolymers, they have obtained acid-dyeable, cationic dye capable of dyeing, the fiber of disperse dye dyeable, and three kinds of fibers that dyestuff all can dye, and Color is good.
(high bridge wise man also for document, the pure hero in nearly field, clear water justice is male. and fiber can be learned will .1994,50 (7): 248-255) with maleic anhydride modified polypropylene (MALEIC ANHYDRIDE content 0.3%wt), and with products therefrom as polypropylene and polyamide blended compatilizer, obtain the good blending and modifying fiber of processibility.This fiber can be used acid dyeing.
Document (permitted the Chifeng, Zheng Limin. the research of acid dyeable polypropylene fibre. the weaving basic science journal .1999 of colleges and universities, 12 (1): 32-35.Permitted the Chifeng, Zheng Limin. the discussion of acid dyeable polypropylene fibre dyeing. the journal .1998 of China Textile University, 24 (5): 104-106) synthesized the multipolymer of diethylenetriamine, hexanodioic acid and nylon salt, and obtained blending and modifying with this multipolymer and polypropene blended and melt-spinning and can dye fiber.The gained modified fibre is good with acid blue BGA, acid scarlet G, bavin woods acid blue 5GM and the red BS Color of caprone, and finds that modified fibre is preferably and dye with weak acid dye.
Though fiber manufacturers all over the world and research unit have carried out a large amount of research to the polypropylene fibre of acid-dyeable, but the polypropylene fibre of acid-dyeable is not yet in the textile industry widespread usage, its major cause is the operational path complexity, consistency difference and cost of material are more high, and therefore further the polypropylene fibre of research and development acid-dyeable will have important social and economic implications.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of polymer with nitrogen that contains allyl group long-chain ester and maleic anhydride monomer and preparation method thereof, to satisfy the needs of relevant department.
The molecular weight of nitrogen-containing copolymer of the present invention is Mw=9 * 10
4～10 * 10
4, structure fragment is as follows:
Wherein:
R represents hydrogen atom or methyl;
R
1Represent C
12～C
20Aliphatic alkyl;
R
2Represent aliphatic alkyl, aromatic hydrocarbons or
In a kind of;
R
4, R
5Represent alkyl, m=3～5.
Preferred R
2Be C
16～C
20Aliphatic alkyl, benzene, preferred R
4, R
5Be methyl or ethyl.
Polymkeric substance of the present invention can be differentiated by infrared spectra, before the analytical test, product dissolves once more with toluene and uses methanol extraction, is dried to constant weight then in vacuum drying oven, remove wherein amine, solvent and catalyzer, to eliminate their influences to analytical test.The infrared spectrum common feature of products therefrom is that multipolymer is originally at 1782.8cm behind the multipolymer imidization
-1And 1854.4cm
-1The acid anhydrides carbonyl feature honeybee that the place occurs disappears, and at 1700cm
-1Near the carbonyl feature honeybee of epimino appears, and the acid amides bands of a spectrum do not appear.
The molecular weight of described polymkeric substance and molecular weight distribution can be measured by gel permeation chromatography (GPC) method.
The preparation method of above-mentioned polymkeric substance comprises the steps:
(1) is comonomer with MALEIC ANHYDRIDE with the monomer that contains vinyl, under the existence and protection of nitrogen gas of initiator, in solvent, carries out copolymerization, obtain multipolymer;
Said initiator is conventional azo-initiator, preferred Diisopropyl azodicarboxylate, and initiator amount is 0.05%～0.5% of a total monomer mole number;
Polymerization temperature is 40 ℃～80 ℃, and the time is 3h～8h, and MALEIC ANHYDRIDE is 1: 0.4～1: 0.8 with the monomer mole ratio that contains vinyl; The preferred toluene of solvent;
The said monomer that contains vinyl is C
12～C
20Methacrylic ester, preferable methyl vinylformic acid carbon 14 esters.
(2) then multipolymer and organic amine are carried out amination or imidization in solvent, make acid anhydrides amidation or imidization and dehydration in the multipolymer, promptly obtain nitrogen-containing copolymer of the present invention.
Temperature of reaction is 40 ℃～80 ℃, and the time is 3h～8h, and multipolymer and organic amine mol ratio are 1: 5～1: 20;
A kind of and composition thereof in the preferred aniline of said organic amine, 3-dimethylamino-1-propylamine or the positive stearylamine, selecting 3-dimethylamino-1-propylamine is in order to introduce more nitrogen-containing group in multipolymer, 3-dimethylamino-1-propylamine and positive stearylamine are mixed use, can when introducing more nitrogen-containing group, also introduce long aliphatic lateral chain.Said solvent comprises toluene, N, N dimethyl formamide or both mixtures; Reaction expression is:
With the purpose of the MALEIC ANHYDRIDE imidization in the polymkeric substance is the acidic-group of wishing to reduce in the polymkeric substance, improves the dye uptake of matching stain, improves the spinning processing performance.
Selecting long alkyl chain methacrylates is to wish that long aliphatic lateral chain can improve multipolymer and polyacrylic consistency.
Multipolymer of the present invention can be used as functional modification auxiliary agent and polypropene blended, spinning, to improve the acid dyeable of polypropylene fibre.
Polymkeric substance of the present invention had both had higher polar group content, with polypropylene consistency is preferably arranged again, so have the dual-use function of acid dyeable and compatilizer concurrently, save the necessary compatilizer of general blending and modifying fiber, adopt simple binary blend, the preparation method is simple, is convenient to suitability for industrialized production.
Description of drawings
Fig. 1 is the infrared spectra of MALEIC ANHYDRIDE and methacrylic acid carbon 14 ester copolymers.
Fig. 2 is the nitrogen-containing copolymer infrared spectra of embodiment 1.
Fig. 3 be embodiment 2 the nitrogen-containing copolymer infrared spectra.
Fig. 4 be embodiment 3 the nitrogen-containing copolymer infrared spectra.
Embodiment
Embodiment 1
Get 70 gram MALEIC ANHYDRIDE, 30 gram methacrylic acid carbon, 14 esters, 0.1 gram Diisopropyl azodicarboxylate places reactor, under nitrogen protection, stirs and is warming up to 60 ℃, reacts 4 hours, obtains multipolymer, and its infared spectrum is seen Fig. 1.
The infrared spectrum of copolymerization product is at 1782.8cm among Fig. 1
-1And 1854.4cm
-1Strong characteristic peak appears in the place, and this should return the symmetry and the asymmetrical stretching vibration peak of the carbonyl (C=O) that belongs to acid anhydrides respectively, and is in the 1782.8cm of low frequency
-1Bands of a spectrum than the 1854.4cm of high frequency
-1Bands of a spectrum are strong, meet the carbonyl feature of five-membered ring shape acid anhydrides, and illustrating has cyclic acid anhydride to exist in the copolymerization product.Two carbonyl characteristic peak wave numbers of acid anhydrides differ about 80cm
-1, meet the feature of unsaturated cyclic anhydride, and be positioned at the 1782.8cm of lower wave number
-1Not division of peak, these 2 acid anhydrides that can be described this moment have not been unsaturated maleic anhydride monomer.In the spectrogram at 1726cm
-1Another carbonylic stretching vibration peak should belong to the ester carbonyl group of methacrylic acid carbon tetradecane ester.In the infrared spectrum of product at 1640cm
-1Near carbon-carbon double bond (C=C) characteristic peak that does not have appearance, illustrating does not have unreacted monomer in the product, at 2924.0cm
-1And 2853.5cm
-1It is the stretching vibration characteristic peak of methylene radical that the place occurs, 1467cm
-1What occur is methylene radical flexural vibration characteristic peaks.Spectrogram is at 3400cm in addition
-1Near the O-H stretching vibration peak does not appear, this can illustrate that methacrylic acid carbon tetradecane ester in the product does not have hydrolysis to form hydroxyl yet.
The above-mentioned multipolymer of 60 grams is inserted 250ml toluene and N, in the mixed solvent of N dimethyl formamide (volume ratio 1: 1), drop into multipolymer, the aniline of 5g is placed constant pressure funnel.Begin to be warming up to 60 ℃, open stirring and make polymer dissolution, treat slowly to drip after polymer dissolution fully amine (about 2h) and react, drip off the about 30min of back continuation reaction.Be warming up to the solution boiling then, carry out imidization and dehydration reaction.Observe the water of collecting in the water segregator, till keeping the reaction liquid boiling in water segregator, not observe having water sepn to come out.Then reaction system is cooled to room temperature, reaction product is come out with methanol extraction, and vacuum-drying.Promptly obtain nitrogen-containing copolymer of the present invention, product is that oyster white has certain flexible solid.
The number-average molecular weight of this nitrogen-containing copolymer is 5.4 ten thousand, and heat decomposition temperature is 366 ℃, and its infared spectrum is seen Fig. 2.The feature of the infrared spectrum of products therefrom is that multipolymer is originally at 1782.8cm behind the multipolymer imidization
-1And 1854.4cm
-1The acid anhydrides carbonyl feature honeybee that the place occurs disappears, and at 1715cm
-1Near the carbonyl characteristic peak of epimino appears, and the acid amides bands of a spectrum do not appear
Embodiment 2
Adopt the identical method of embodiment 1, replace aniline with 4.5 gram 3-dimethylaminos-1-propylamine, the number-average molecular weight of this nitrogen-containing copolymer is 5.2 ten thousand, and heat decomposition temperature is 358 ℃, on its infared spectrum 1715cm is arranged
-1The characteristic peak of the carbonyl characteristic peak of epimino is seen Fig. 3.
Embodiment 3
Get 60 gram MALEIC ANHYDRIDE, 40 gram methacrylic acid carbon, ten diester, 0.12 gram Diisopropyl azodicarboxylate places reactor, under nitrogen protection, stirs and is warming up to 80 ℃, reacts 3 hours, obtains multipolymer;
With the above-mentioned multipolymer of 50 grams, 3 gram 3-dimethylamino-1-propylamine, the positive stearylamine of 3 grams is dissolved in 250ml N, and in the N dimethyl formamide, reaction is 3 hours under 80 ℃ temperature, carries out imidization and dehydration, promptly obtains nitrogen-containing copolymer of the present invention.
The number-average molecular weight of this nitrogen-containing copolymer is 5.5 ten thousand, and heat decomposition temperature is 358 ℃, on its infared spectrum 1715cm is arranged
-1The characteristic peak of the carbonyl characteristic peak of epimino is seen Fig. 4.
Claims (10)
1. polymer with nitrogen that contains allyl group long-chain ester and maleic anhydride monomer is characterized in that structure fragment is as follows:
Wherein:
R represents hydrogen atom or methyl;
R
1Represent C
12～C
20Aliphatic alkyl;
R
2Represent aliphatic alkyl, aromatic hydrocarbons or
In a kind of;
R
4, R
5Represent alkyl, m=3～5.
2. polymer with nitrogen according to claim 1 is characterized in that R
2Be C
16～C
20Aliphatic alkyl, phenyl, R
4, R
5Be methyl or ethyl.
3. the preparation method of polymer with nitrogen according to claim 1 and 2 is characterized in that, comprises the steps:
(1) is comonomer with MALEIC ANHYDRIDE with the monomer that contains vinyl, under the existence and protection of nitrogen gas of initiator, carries out copolymerization, obtain multipolymer;
Polymerization temperature is 40 ℃～80 ℃, and the time is 3～8h,
The said monomer that contains vinyl is C
12～C
20Methacrylic ester;
(2) then multipolymer and organic amine are carried out amination or imidization in solvent, make acid anhydrides amidation or imidization and dehydration in the multipolymer, promptly obtain nitrogen-containing copolymer of the present invention;
Temperature of reaction is 40 ℃～80 ℃, and the time is 2～6h.
4. method according to claim 3 is characterized in that, initiator is a Diisopropyl azodicarboxylate.
5. method according to claim 3 is characterized in that, the said monomer that contains vinyl is methacrylic acid carbon 14 esters.
6. method according to claim 3 is characterized in that, MALEIC ANHYDRIDE is 1: 0.4～1: 0.8 with the monomer mole ratio that contains vinyl.
7. method according to claim 3 is characterized in that, said organic amine comprises a kind of and composition thereof in aniline, 3-dimethylamino-1-propylamine or the positive stearylamine.
8. method according to claim 7 is characterized in that, said organic amine is the mixture of 3-dimethylamino-1-propylamine and positive stearylamine.
9. method according to claim 3 is characterized in that, multipolymer and organic amine mol ratio are 1: 5～1: 20.
10. method according to claim 3 is characterized in that said solvent comprises toluene, N, N dimethyl formamide or the mixture of the two.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031418295A CN100400559C (en) | 2003-07-24 | 2003-07-24 | Nitrogenous polymer containing long-chain allyl ester and maleic anhydride monomer and its prepn |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031418295A CN100400559C (en) | 2003-07-24 | 2003-07-24 | Nitrogenous polymer containing long-chain allyl ester and maleic anhydride monomer and its prepn |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1486997A true CN1486997A (en) | 2004-04-07 |
| CN100400559C CN100400559C (en) | 2008-07-09 |
Family
ID=34155479
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031418295A Expired - Fee Related CN100400559C (en) | 2003-07-24 | 2003-07-24 | Nitrogenous polymer containing long-chain allyl ester and maleic anhydride monomer and its prepn |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100400559C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1302031C (en) * | 2005-03-25 | 2007-02-28 | 泰山玻璃纤维股份有限公司 | Use of methacrylic acid tetradecyl ester-maleic anhydride copolymer |
| WO2012013432A1 (en) * | 2010-07-29 | 2012-02-02 | Evonik Rohmax Additives Gmbh | Polyalkyl (meth) acrylate for improving lubricating oil properties |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR9507945A (en) * | 1994-06-07 | 1997-09-02 | Lyondell Petrochem | Tintable polyolefin compositions and process |
| JP3615103B2 (en) * | 1999-11-18 | 2005-01-26 | 日本製紙株式会社 | Modified polyolefin composition and use thereof |
| KR100568533B1 (en) * | 2000-12-20 | 2006-04-07 | 주식회사 효성 | Easily dyed polypropylene, method for preparing thereof and polypropylene composition comprising thereof |
| CN1155658C (en) * | 2001-09-06 | 2004-06-30 | 林福海 | Dyeable polypropylene fiber grain and its production process |
-
2003
- 2003-07-24 CN CNB031418295A patent/CN100400559C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1302031C (en) * | 2005-03-25 | 2007-02-28 | 泰山玻璃纤维股份有限公司 | Use of methacrylic acid tetradecyl ester-maleic anhydride copolymer |
| WO2012013432A1 (en) * | 2010-07-29 | 2012-02-02 | Evonik Rohmax Additives Gmbh | Polyalkyl (meth) acrylate for improving lubricating oil properties |
| US9777098B2 (en) | 2010-07-29 | 2017-10-03 | Evonik Oil Additives Gmbh | Polyalkyl(meth)acrylate for improving lubricating oil properties |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100400559C (en) | 2008-07-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101200544B (en) | Amine-terminated hyperbranced compound quaternary ammonium salt and preparation method thereof | |
| CN1919893A (en) | Hyperbranched great macromonomer, acrylate resin containing hyperbranched structure and preparation method | |
| Iwakura et al. | Reactive fiber. Part I. Copolymerization and copolymer of acrylonitrile with glycidyl methacrylate and with glycidyl acrylate | |
| CN101078183A (en) | Super-branching reactive dye salt-free dyeing auxiliary | |
| Kim et al. | Reactive dyeing of meta-aramid fabrics photografted with dimethylaminopropyl methacrylamide | |
| CN1486997A (en) | Nitrogenous polymer containing long-chain allyl ester and maleic anhydride monomer and its prepn | |
| CN109295523B (en) | Permanent antistatic acrylonitrile-based copolymer and preparation method of fiber thereof | |
| CN115787132A (en) | Preparation method of creep-resistant polyester industrial yarn | |
| CN1683617A (en) | Modified polytrimethylene terephthalate fiber and preparation method thereof | |
| CN1142952C (en) | Polyacrylonitrile polymer treatment | |
| CN115595808A (en) | Dyeing method of cotton fabric by using active dye in non-aqueous medium | |
| CN111072850B (en) | Fluorescent molecular monomer and preparation method thereof, aggregation-induced emission hydrogel and preparation method and application thereof | |
| CN1831022A (en) | Fluorine-contg. block copolymers of pH-responsed and its prepn. method | |
| CN1233772C (en) | Durable anti-static agent for acrylic fiber | |
| Somanathan et al. | Syhthesis of Casein Graft Poly (acrylonitrile) | |
| CN111229137A (en) | Feather polypeptide modified polyacrylate fiber aerogel and preparation method and application thereof | |
| Chen et al. | Synthesis and characterization of new acrylic polymer containing silk protein | |
| US2643992A (en) | Fiber-forming polmers | |
| Dayioglu | Polymeric dye receptors for disperse dyeable polypropylene fibers | |
| US2719134A (en) | Mixtures comprising acrylonitrile polymers with polymeric phosphonic acid diamides | |
| CN113831465B (en) | Amphoteric organosilicon modified acrylic resin retanning agent and preparation method thereof | |
| CN114716685B (en) | Polycarboxylic acid dispersant, preparation method thereof, polycarboxylic acid dispersant and application | |
| CN111534096B (en) | Self-repairing thermoplastic elastomer sheath material and preparation method thereof | |
| CN117403341B (en) | Preparation method of polyacrylic fiber with high stretching ratio | |
| CN116791380A (en) | Reactive dye auxiliary agent with high color fastness and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080709 |