CN100400559C - 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
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- CN100400559C CN100400559C CNB031418295A CN03141829A CN100400559C CN 100400559 C CN100400559 C CN 100400559C CN B031418295 A CNB031418295 A CN B031418295A CN 03141829 A CN03141829 A CN 03141829A CN 100400559 C CN100400559 C CN 100400559C
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Abstract
The present invention relates to a nitrogenous polymer containing allyl long-chain ester and maleic anhydride monomer and a preparation method thereof. The polymer preparation method comprises the following procedures: maleic anhydride monomers and monomers containing ethylene are used as co-monomers to carry out coyolymerization to obtain copolymers; then, the copolymers and organic amine carry out amination or imidization in solvent, and the nitrogenous polymer of the present invention is obtained. The polymer of the present invention can be used as functional modifying addition agents to be mixed with polypropylene for spinning in order to improve the acidic dyeability of polypropylene fiber. The polymer of the present invention has high polar group contents as well as good compatibility with the polypropylene, so the polymer has the dual functions of acid dyeability and compatilizer effect, and compatilizer required by common blending modified fiber is saved. Simple binary blending is adopted, so the preparation method is simple and convenient for commercial production. The structural details of the nitrogenous polymer of the present invention are shown in the specifications.
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) has 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
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 (6)
1. the preparation method of polymer with nitrogen 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;
Temperature of reaction is 40 ℃～80 ℃, and the time is 3～8h;
MALEIC ANHYDRIDE is 1: 0.4～1: 0.8 with the monomer mole ratio that contains vinyl;
Multipolymer and organic amine mol ratio are 1: 5～1: 20.
2. method according to claim 1 is characterized in that, initiator is a Diisopropyl azodicarboxylate.
3. method according to claim 1 is characterized in that, the said monomer that contains vinyl is methacrylic acid carbon 14 esters.
4. method according to claim 1 is characterized in that, said organic amine comprises a kind of and composition thereof in aniline, 3-dimethylamino-1-propylamine or the positive stearylamine.
5. method according to claim 4 is characterized in that, said organic amine is the mixture of 3-dimethylamino-1-propylamine and positive stearylamine.
6. method according to claim 1 is characterized in that said solvent is selected from toluene, N, N dimethyl formamide or the mixture of the two.
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|---|---|---|---|
| CNB031418295A CN100400559C (en) | 2003-07-24 | 2003-07-24 | Nitrogenous polymer containing long-chain allyl ester and maleic anhydride monomer and its prepn |
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|---|---|---|---|
| CNB031418295A CN100400559C (en) | 2003-07-24 | 2003-07-24 | Nitrogenous polymer containing long-chain allyl ester and maleic anhydride monomer and its prepn |
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| CN1486997A CN1486997A (en) | 2004-04-07 |
| CN100400559C true CN100400559C (en) | 2008-07-09 |
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| 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 |
| DE102010038615A1 (en) * | 2010-07-29 | 2012-02-02 | Evonik Rohmax Additives Gmbh | Polyalkyl (meth) acrylate for improving lubricating oil properties |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1157015A (en) * | 1994-06-07 | 1997-08-13 | 莱昂德尔石油化学公司 | Dyeable polyolefin compositions and method |
| EP1101779A1 (en) * | 1999-11-18 | 2001-05-23 | Nippon Paper Industries Co., Ltd. | Modified polyolefin composition and uses thereof |
| CN1337424A (en) * | 2001-09-06 | 2002-02-27 | 林福海 | Dyeable polypropylene fiber grain and its production process |
| KR20020049852A (en) * | 2000-12-20 | 2002-06-26 | 조정래 | Easily dyed polypropylene, method for preparing thereof and polypropylene composition comprising thereof |
-
2003
- 2003-07-24 CN CNB031418295A patent/CN100400559C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1157015A (en) * | 1994-06-07 | 1997-08-13 | 莱昂德尔石油化学公司 | Dyeable polyolefin compositions and method |
| EP1101779A1 (en) * | 1999-11-18 | 2001-05-23 | Nippon Paper Industries Co., Ltd. | Modified polyolefin composition and uses thereof |
| KR20020049852A (en) * | 2000-12-20 | 2002-06-26 | 조정래 | Easily dyed polypropylene, method for preparing thereof and polypropylene composition comprising thereof |
| CN1337424A (en) * | 2001-09-06 | 2002-02-27 | 林福海 | Dyeable polypropylene fiber grain and its production process |
Non-Patent Citations (4)
| Title |
|---|
| Dyeing polypropylene fibers by means of copolymer additives. Hong, Sung II, Kim, Sung Tae, Lee, Taek Seung.J. Soc. Dyers Colour,No.110. 1994 |
| Dyeing polypropylene fibers by means of copolymer additives. Hong, Sung II, Kim, Sung Tae, Lee, Taek Seung.J. Soc. Dyers Colour,No.110. 1994 * |
| 聚丙烯纤维着色技术进展. 刘俊龙，张淑芬，杨锦宗.化工进展，第3期. 2000 |
| 聚丙烯纤维着色技术进展. 刘俊龙，张淑芬，杨锦宗.化工进展，第3期. 2000 * |
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