CN100400559C - Nitrogen-containing polymer containing allyl long-chain ester and maleic anhydride monomer and its preparation method - Google Patents

Abstract

The invention relates to a nitrogen-containing polymer containing allyl long-chain ester and maleic anhydride monomer and a preparation method thereof. The preparation method of the polymer comprises the following steps: (1) taking maleic anhydride and vinyl-containing monomers as comonomers to carry out copolymerization to obtain a copolymer; (2) then mixing the copolymer and an organic amine in a solvent Amination or imidization is carried out to obtain the nitrogen-containing copolymer of the present invention. The polymer of the invention can be used as a functional modification auxiliary agent to blend and spin with polypropylene to improve the acid dyeability of polypropylene fibers. The polymer of the present invention not only has a higher polar group content, but also has better compatibility with polypropylene, so it has the dual functions of acid dyeable and compatibilizer, and saves the need for general blended modified fiber The necessary compatibilizer adopts simple binary blending, the preparation method is simple, and the industrial production is convenient. The structural fragments of the nitrogen-containing copolymer of the present invention are as follows.

Description

Nitrogen-containing polymer containing allyl long-chain ester and maleic anhydride monomer and its preparation method

technical field

The invention relates to a nitrogen-containing polymer containing allyl long-chain ester and maleic anhydride monomer and a preparation method thereof, in particular to a polymer for improving the dyeability of polypropylene fibers.

Background technique

The acid-dyeable modification of polypropylene fiber is a difficult problem that has not been completely solved so far. For this reason, many scientific and technical personnel have done a lot of research work. Among the various methods to improve the dyeing properties of polypropylene fibers, the blending method is the most feasible method for industrial application, and it is also the direction of related research. The choice of which copolymer to blend with polypropylene determines which type of dye the blended modified fiber can be dyed and the properties of the fiber. It can also be used as a compatibilizer to make polypropylene polymerize with another more polar polymer. material blending.

J.Akrman and his colleagues have done a lot of exploratory work in the research of acid dyeable polypropylene fibers. The blending additives they use are derivatives of maleic anhydride-styrene copolymers (using 3-dimethyl Aminopropylamine, octadecylamine and 3-morpholinopropylamine imidate maleic anhydride), blended and melt-spun to obtain acid dyeable polypropylene fibers, and achieved good results.

The document "Dyeing polypropylene fibers by means of copolymer additives" (J.S.D.C.1994, 110:19-23) discloses three kinds of copolymers, which are composed of stearyl methacrylate and (a) maleic anhydride respectively; b) N-substituted ((dimethylamino) propyl) acrylamide; (c) copolymerization of maleic acid hydrazide, these three copolymers are used alone or mixed with polypropylene and melt-spun, they Fibers dyeable with acid dyes, cationic dyes, and disperse dyes, and fibers dyeable with all three kinds of dyes are obtained, and the dyeing effect is good.

Literature (Takahashi Tetsuya, Konda Junxiong, Shimizu Yoshio. Journal of Fiber Society. 1994, 50(7): 248-255) Modified polypropylene with maleic anhydride (maleic anhydride content 0.3%wt) , and the obtained product is used as a compatibilizer for blending polypropylene and polyamide to obtain a blended modified fiber with good processability. This fiber can be dyed with acid dyes.

Literature (Xu Chifeng, Zheng Limin. Research on acid-dyeable polypropylene fiber. Basic Science Journal of Textile Universities. 1999, 12(1): 32-35. Xu Chifeng, Zheng Limin. Discussion on the dyeing process of acid-dyeable polypropylene fiber. Journal of China Textile University. 1998, 24(5): 104-106) synthesized a copolymer of diethylenetriamine, adipic acid and nylon 66 salt, and blended the copolymer with polypropylene and melt spun to obtain a blended modified dyeable fiber . The obtained modified fiber has good dyeing effect with acid blue BGA, acid scarlet G, Chailin Lake blue 5GM and Capron red BS, and it is found that the modified fiber is more suitable for dyeing with weak acid dyes.

Although fiber manufacturers and research institutes around the world have conducted a lot of research on acid dye-dyeable polypropylene fibers, acid dye-dyeable polypropylene fibers are still not widely used in the textile industry. The main reason is that the process route is complicated. , poor compatibility and high raw material prices, etc., so further research and development of polypropylene fibers dyeable with acid dyes will have great social and economic significance.

Contents of the invention

The technical problem to be solved in the present invention is to disclose a nitrogen-containing polymer containing allyl long-chain ester and maleic anhydride monomer and its preparation method to meet the needs of relevant departments.

The molecular weight of the nitrogen-containing copolymer of the present invention is Mw=9×10 ⁴ ~10×10 ⁴ , and the structural fragments are as follows:

in:

R represents a hydrogen atom or a methyl group;

R ₁ represents C ₁₂ ~ C ₂₀ aliphatic alkyl;

中的一种；R ₂ represents aliphatic alkyl, aromatic hydrocarbon or

one of

R ₄ and R ₅ represent an alkyl group, and m=3-5.

Preferred R ₂ is a C ₁₆ -C ₂₀ aliphatic alkyl group or benzene, preferred R ₄ and R ₅ are methyl or ethyl.

The polymer of the present invention can be identified by infrared spectroscopy. Before the analysis test, the product is redissolved with toluene and precipitated with methanol, and then dried to constant weight in a vacuum oven to remove amines, solvents and catalysts therein to eliminate their impact on the analysis test. Impact. The common feature of the infrared spectra of the products obtained after the imidization of the copolymer is that the carbonyl feature of the acid anhydride that appeared at 1782.8cm ^-1 and 1854.4cm ^-1 of the copolymer disappeared, and the cyclic imine appeared around 1700cm ^-1 Carbonyl characteristic bee, and no amide band appears.

The molecular weight and molecular weight distribution of the polymer can be determined by gel permeation chromatography (GPC) method.

The preparation method of above-mentioned polymer comprises the steps:

(1) using maleic anhydride and vinyl-containing monomers as comonomers, in the presence of an initiator and under the protection of nitrogen, carry out copolymerization in a solvent to obtain a copolymer;

The initiator is a conventional azo initiator, preferably azobisisobutyronitrile, and the amount of the initiator is 0.05% to 0.5% of the total monomer moles;

The polymerization temperature is 40°C-80°C, the time is 3h-8h, the molar ratio of maleic anhydride to vinyl-containing monomer is 1:0.4-1:0.8; the solvent is preferably toluene;

The vinyl-containing monomer is C ₁₂ -C ₂₀ methacrylate, preferably carbon tetradecyl methacrylate.

(2) The copolymer and the organic amine are then aminated or imidized in a solvent to make the acid anhydride in the copolymer amidated or imidized and dehydrated to obtain the nitrogen-containing copolymer of the present invention.

The reaction temperature is 40°C-80°C, the time is 3h-8h, and the molar ratio of the copolymer to the organic amine is 1:5-1:20;

Said organic amine is preferably one of aniline, 3-dimethylamino-1-propylamine or n-octadecylamine and a mixture thereof, and 3-dimethylamino-1-propylamine is selected for introducing more For more nitrogen-containing groups, the mixed use of 3-dimethylamino-1-propylamine and n-octadecylamine can introduce long aliphatic side chains while introducing more nitrogen-containing groups. Said solvent comprises toluene, N, N dimethylformamide or the mixture of the two; General reaction formula is:

The purpose of imidizing the maleic anhydride in the polymer is to reduce the acidic groups in the polymer, increase the dye uptake rate of acid dyes, and improve the spinning performance.

The long-chain methacrylate is selected in the hope that the longer aliphatic side chain can improve the compatibility of the copolymer with polypropylene.

The copolymer of the invention can be used as a functional modification auxiliary agent to blend and spin with polypropylene to improve the acid dyeability of polypropylene fibers.

The polymer of the present invention not only has a higher polar group content, but also has better compatibility with polypropylene, so it has the dual functions of acid dyeable and compatibilizer, and saves the need for general blended modified fiber The necessary compatibilizer adopts simple binary blending, the preparation method is simple, and the industrial production is convenient.

Description of drawings

Fig. 1 is the infrared spectrum of maleic anhydride and carbon tetradecyl methacrylate copolymer.

Fig. 2 is the infrared spectrum of the nitrogen-containing copolymer of embodiment 1.

Fig. 3 is the infrared spectrum of the nitrogen-containing copolymer of embodiment 2.

Fig. 4 is the infrared spectrum of the nitrogen-containing copolymer of embodiment 3.

Detailed ways

Example 1

Take 70 grams of maleic anhydride, 30 grams of tetradecyl methacrylate, and 0.1 gram of azobisisobutyronitrile, put them in a reactor, and under the protection of nitrogen, stir and heat up to 60° C., and react for 4 hours to obtain Copolymer, its infrared spectrum is shown in Figure 1.

The infrared spectrogram of the copolymerization product in Fig. 1 presents strong characteristic peaks at 1782.8cm ^-1 and 1854.4cm ^-1 , which should be attributed to the symmetry and asymmetry stretching vibration peaks of the carbonyl (C=O) of the acid anhydride respectively, and are in The low-frequency 1782.8cm ^-1 band is stronger than the high-frequency 1854.4cm ^-1 band, which is consistent with the carbonyl characteristics of five-membered cyclic anhydrides, indicating that there are cyclic anhydrides in the copolymerization product. The wavenumber difference between the two carbonyl characteristic peaks of the acid anhydride is about 80cm ^-1 , which is consistent with the characteristics of a saturated cyclic anhydride, and the peak at 1782.8cm ^-1 at a low wavenumber is not split. These two points can indicate that the acid anhydride is no longer unsaturated butenedioic anhydride monomer. Another carbonyl stretching vibration peak at 1726cm ^-1 in the spectrum should be attributed to the ester carbonyl of carbastetradecyl methacrylate. In the infrared spectrum of the product, there is no characteristic peak of carbon-carbon double bond (C=C) near 1640cm ^{-1 ,} indicating that there is no unreacted monomer in the product, and ^it is sub- The characteristic peak of the stretching vibration of the methyl group, the characteristic peak of the bending vibration of the methylene group appears at 1467cm ^{- 1} . In addition, there is no OH stretching vibration peak around 3400 cm ^-1 in the spectrum, which can explain that the carbastetradecyl methacrylate in the product has not been hydrolyzed to form hydroxyl groups.

Put 60 grams of the above copolymer into 250 ml of a mixed solvent of toluene and N, N dimethylformamide (volume ratio 1:1), put into the copolymer, and place 5 g of aniline in a constant pressure dropping funnel. Start to heat up to 60°C, start stirring to dissolve the polymer, and slowly add amine dropwise (about 2 hours) to react after the polymer is completely dissolved, and continue to react for about 30 minutes after the drop is completed. Then the temperature is raised until the solution boils for imidization and dehydration reactions. Observe the water collected in the moisture trap, and keep the reaction liquid boiling until no water separation is observed in the moisture trap. Then the reaction system was cooled to room temperature, and the reaction product was precipitated with methanol and dried in vacuo. That is, the nitrogen-containing copolymer of the present invention is obtained, and the product is a milky white solid with certain toughness.

The number-average molecular weight of the nitrogen-containing copolymer is 54,000, and its thermal decomposition temperature is 366°C. Its infrared spectrum is shown in Fig. 2 . The characteristic of the infrared spectrum of the product obtained after the imidization of the copolymer is that the carbonyl characteristic of the acid anhydride that originally appeared in the copolymer at 1782.8cm ^-1 and 1854.4cm ^-1 disappeared, and the carbonyl of the cyclic imide appeared near 1715cm ^-1 Characteristic peaks and no amide bands

Example 2

Using the same method as in Example 1, replacing aniline with 4.5 grams of 3-dimethylamino-1-propylamine, the number-average molecular weight of this nitrogen-containing copolymer is 52,000, and its thermal decomposition temperature is 358° C. The characteristic peak of the carbonyl characteristic peak of ^-1 cyclic imine is shown in Figure 3.

Example 3

Take 60 grams of maleic anhydride, 40 grams of carbon dodecyl methacrylate, and 0.12 grams of azobisisobutyronitrile, place them in a reactor, and under nitrogen protection, stir and heat up to 80° C., and react for 3 hours to obtain copolymer;

50 grams of the above-mentioned copolymer, 3 grams of 3-dimethylamino-1-propylamine, and 3 grams of n-octadecylamine were dissolved in 250 ml of N, N dimethylformamide, and reacted for 3 hours at a temperature of 80 ° C. Imination and dehydration can obtain the nitrogen-containing copolymer of the present invention.

The nitrogen-containing copolymer has a number-average molecular weight of 55,000 and a thermal decomposition temperature of 358°C. Its infrared spectrum has a characteristic peak of the carbonyl characteristic peak of 1715cm ⁻¹ cyclic imine, as shown in 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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