阅读说明：本技术 一种易染改性间位芳纶及其制备方法 (It is a kind of easily to contaminate modified meta-aramid and preparation method thereof ) 是由 关振虹 宋金苓 潘士东 陈延平 李丹 于 2019-08-30 设计创作，主要内容包括：本发明公开了一种易染改性间位芳纶及其制备方法,该方法以间苯二甲酰氯、间苯二胺、3,5-二氨基苯甲酸钠和双(3-氨基苯基)苯基氧化磷为单体,在有机溶剂中采用低温缩聚制备改性聚间苯二甲酰间苯二胺纺丝溶液,制成的纤维对阳离子染料有良好的亲和性以及优良的阻燃性；制备过程中加入含有羧酸基团的3,5-二氨基苯甲酸单体参与共聚,羧酸基团为阴离子基团,可以与阳离子染料以离子键结合,实现阳离子染料易染。本发明制备的易染改性间位芳纶的纺丝原液具有良好的溶解性、可纺性,制成纤维保持原有的耐高温以及力学性能,并且在阳离子染料中上染率较高,颜色亮丽,耐光牢度好。(Modified meta-aramid and preparation method thereof is easily contaminated the invention discloses a kind of, this method is with m-phthaloyl chloride, m-phenylene diamine (MPD), 3,5- diaminobenzoic acid sodium and bis- (3- aminophenyl) phenylphosphine oxides are monomer, modified poly (m-phenylene isophthalmide) spinning dope is prepared using low-temperature polycondensation in organic solvent, manufactured fiber has good compatibility and excellent anti-flammability to the dye of positive ion；3,5- diaminobenzoic acid monomer containing carboxylic acid group is added in preparation process and participates in copolymerization, carboxylic acid group is anionic group, can with the dye of positive ion with ionic bond in conjunction with, realize cation dye chromophil.The easy spinning solution for contaminating modified meta-aramid prepared by the present invention has good dissolubility, spinnability, and fiber is made and keeps original high temperature resistant and mechanical property, and dye-uptake is higher in the dye of positive ion, color is beautiful, and fastness to light is good.)

1. a kind of easily contaminate modified meta-aramid, which is characterized in that chemical structural formula are as follows:

Wherein: 5≤X≤10,1≤Y≤5,85≤Z≤94.

2. a kind of preparation method for easily contaminating modified meta-aramid, which is characterized in that preparation process are as follows: by m-phenylene diamine (MPD), isophthalic two Formyl chloride, 3,5- diaminobenzoic acid sodium and bis- (3- aminophenyl) phenylphosphine oxides are added into organic solvent, and polycondensation occurs Modified poly (m-phenylene isophthalmide) spinning dope is obtained after reaction；Then it is made by wet spinning and easily contaminates modified meta position virtue Synthetic fibre precursor will easily contaminate drying, thermal finalization after modified meta-aramid precursor washing, and be made and easily contaminate modified meta-aramid.

3. a kind of preparation method for easily contaminating modified meta-aramid according to claim 2, which is characterized in that described organic molten Agent is one of N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone and dimethyl sulfoxide or several Kind.

4. a kind of preparation method for easily contaminating modified meta-aramid according to claim 2, which is characterized in that the modification is poly- The viscosity of (m-phenylene isophthalmide) spinning dope is 40~70Pas.

5. a kind of preparation method for easily contaminating modified meta-aramid according to claim 2, which is characterized in that m-phenylene diamine (MPD), M-phthaloyl chloride, 3,5- diaminobenzoic acid sodium and bis- (3- aminophenyl) phenylphosphine oxide polycondensation reactions in organic solvent Detailed process are as follows:

Step 1, m-phenylene diamine (MPD), 3,5- diaminobenzoic acid sodium and bis- (3- aminophenyl) phenyl are added in organic solvent to aoxidize Reaction system after stirring and dissolving, is cooled to -20~-10 DEG C, forms system A by phosphorus；

Step 2, m-phthaloyl chloride is added in two portions in system A, is added in m-phthaloyl chloride and reaction process, entire body Be A temperature control at -20~-10 DEG C, generation structure B after reaction, system B is warming up to 1~3 DEG C, when pole-climbing occurs in system B When phenomenon, polycondensation reaction terminates, and forms system C；Neutralizer is added in system C, the pH value of system C is adjusted to 6-8, is added During neutralizer, temperature≤80 DEG C of system C ultimately generate modified poly (m-phenylene isophthalmide) spinning dope.

6. a kind of preparation method for easily contaminating modified meta-aramid according to claim 5, which is characterized in that in step 1, The molar ratio of phenylenediamine, 3,5- diaminobenzoic acid sodium and bis- (3- aminophenyl) phenylphosphine oxides is (85~94): (1~5): (5~10).

7. a kind of preparation method for easily contaminating modified meta-aramid according to claim 5, which is characterized in that in step 2, M-phenylene diamine (MPD), 3,5- diaminobenzoic acid sodium and the oxidation of bis- (3- aminophenyl) phenyl being added in phthalyl chloride and step 1 The molar ratio of phosphorus total amount is (1.002~1.01): 1；The quality that m-phthaloyl chloride is added for the first time accounts for the 30- that total amount is added 70%.

8. a kind of preparation method for easily contaminating modified meta-aramid according to claim 5, which is characterized in that the neutralizer For calcium hydroxide or liquefied ammonia.

9. a kind of preparation method for easily contaminating modified meta-aramid according to claim 2, which is characterized in that drying temperature is 120~180 DEG C, it is dried to fiber moisture < 5%.

10. a kind of preparation method for easily contaminating modified meta-aramid according to claim 2, which is characterized in that thermal finalization temperature Degree is 200~400 DEG C, and hot-stretch multiple is 1.5~4 times, thermal finalization to meta-aramid stable molding.

[technical field]

The invention belongs to meta-aramid technical fields, and in particular to a kind of easily to contaminate modified meta-aramid and preparation method thereof.

[background technique]

Meta-aramid is one of the high-performance fiber being most widely used, with excellent heat-resisting quantity, anti-flammability, power Performance, electrical insulating property and good textile processibility are learned, is widely applied in protective garment, high-temperature-resistant filtering material, field of compound material. Clothes as special industries such as fire-fightings, it is desirable that special mark and color, but molecular structure is close in meta-aramid fibers, Glass transition temperature is 270 DEG C, even if the individual dyes upper reluctantly of common staining method, but poor color fastness.Industrially adopt mostly Coloured meta-aramid is prepared with the method for original liquid coloring, that is, adds dye to poly (m-phenylene isophthalmide) spinning dope In, if CN100422401C the and CN10240024 2B method for being all made of original liquid coloring prepares coloured meta-aramid, but stoste There are some problems for the method for coloring, if original liquid coloring production method is not flexible, complex process when replacing fiber color, and pipe Road cleaning is difficult, slurry waste etc..

Molecular structure by changing meta-aramid reaches the research for improving dyeability, such as US4278779 and Third monomer meta position xylylene amine is introduced in CN107814928A, US4278779, prepares modified two formyl isophthalic of meta position Diamines carries out spinning, the fibre of this method preparation after mixing later with unmodified poly (m-phenylene isophthalmide) spinning dope Dimension has preferable colourability, but since the relative molecular mass of modified poly is lower, the fibre of preparation Tie up strength reduction.In other related patents or technology, there is the meta-aramid anti-flammability reduction prepared or material purity not Good technical problem is not easy to realize industrialized production.

[summary of the invention]

It is an object of the invention to overcome the above-mentioned prior art, a kind of easily contaminate is provided and is modified meta-aramid and its system Preparation Method；This method and material are for solving the technical issues of dyestuff difficulty is big, fibre strength is low and poor flame retardant properties.

In order to achieve the above objectives, the present invention is achieved by the following scheme:

It is a kind of easily to contaminate modified meta-aramid, chemical structural formula are as follows:

Wherein: 5≤X≤10,1≤Y≤5,85≤Z≤94.

A kind of easy preparation method for contaminating modified meta-aramid, preparation process are as follows: by m-phenylene diamine (MPD), m-phthaloyl chloride, 3, 5- diaminobenzoic acid sodium and bis- (3- aminophenyl) phenylphosphine oxides are added into organic solvent, obtain after polycondensation reaction occurs Modified poly (m-phenylene isophthalmide) spinning dope；Then it is made by wet spinning and easily contaminates modified meta-aramid precursor, it will Drying, thermal finalization after being modified the washing of meta-aramid precursor are easily contaminated, the modified meta-aramid of easily dye is made.

A further improvement of the present invention is that:

Preferably, the organic solvent is n,N-Dimethylformamide, n,N-dimethylacetamide, N-Methyl pyrrolidone One or more of with dimethyl sulfoxide.

Preferably, the viscosity of the modified poly (m-phenylene isophthalmide) spinning dope is 40~70Pas.

Preferably, m-phenylene diamine (MPD), m-phthaloyl chloride, 3,5- diaminobenzoic acid sodium and bis- (3- aminophenyl) phenyl oxygen Change the detailed process of phosphorus polycondensation reaction in organic solvent are as follows:

Step 1, m-phenylene diamine (MPD), 3,5- diaminobenzoic acid sodium and bis- (3- aminophenyl) phenyl are added in organic solvent Reaction system after stirring and dissolving, is cooled to -20~-10 DEG C, forms system A by phosphorous oxide；

Step 2, m-phthaloyl chloride is added in two portions in system A, is added in m-phthaloyl chloride and reaction process, it is whole The temperature of a system A is controlled at -20~-10 DEG C, generation structure B after reaction, and system B is warming up to 1~3 DEG C, when system B occurs When rod climbing phenomenon, polycondensation reaction terminates, and forms system C；Neutralizer is added in system C, the pH value of system C is adjusted to 6-8, It is added during neutralizer, temperature≤80 DEG C of system C ultimately generate modified poly (m-phenylene isophthalmide) spinning dope.

Preferably, in step 1, m-phenylene diamine (MPD), 3,5- diaminobenzoic acid sodium and bis- (3- aminophenyl) phenylphosphine oxides Molar ratio be (85~94): (1~5): (5~10).

Preferably, in step 2, the m-phenylene diamine (MPD), 3, the 5- diaminobenzoic acid sodium that are added in m-phthaloyl chloride and step 1 And the molar ratio of bis- (3- aminophenyl) phenylphosphine oxide total amounts is (1.002~1.01): 1；M-phthaloyl chloride adds for the first time The quality entered accounts for the 30-70% that total amount is added.

Preferably, the neutralizer is calcium hydroxide or liquefied ammonia.

Preferably, drying temperature is 120~180 DEG C, is dried to fiber moisture < 5%.

Preferably, heat setting temperature is 200~400 DEG C, and hot-stretch multiple is 1.5~4 times, and thermal finalization is steady to meta-aramid Fixed molding.

Compared with prior art, the invention has the following advantages:

Modified meta-aramid is easily contaminated the invention discloses a kind of, which introduces sodium carboxylate groups in strand With phosphorous oxide group, two types monomer all has the industrial goods of high-purity, can satisfy needs of production.In fibre structure On, compared with conventional meta-aramid, in fiber molecule chain have anionic group carboxylate radical, can occur with the dye of positive ion from Sub-key effect, can by dye of positive ion molecule " grasping " on strand, reinforcing fiber to " saturation " of the dye of positive ion, To improve fiber dye-uptake and color fastness.The introducing of phosphorous oxide monomer can destroy original poly Molecule ordered structure increases the porosity between molecule, improves the accommodation space of dye molecule, while P elements are fire retardants The promotion of flame retardant property can be protected and be promoted to common element.The easy spinning solution for contaminating modified meta-aramid prepared by the present invention With good dissolubility, spinnability, fiber is made and keeps original fire-retardant and mechanical property, and in the dye of positive ion Dye-uptake is higher, and color is beautiful, and fastness to light is good.

The invention also discloses a kind of preparation method for easily contaminating modified meta-aramid, this method with m-phthaloyl chloride, Phenylenediamine, 3,5- diaminobenzoic acid sodium and bis- (3- aminophenyl) phenylphosphine oxides are monomer, in organic solvent using low Warm polycondensation prepares modified poly (m-phenylene isophthalmide) spinning dope, and manufactured fiber has the dye of positive ion good affine Property and excellent anti-flammability；3, the 5- diaminobenzoic acid monomer containing carboxylic acid group is added in preparation process and participates in copolymerization, Carboxylic acid group is anionic group, can with the dye of positive ion with ionic bond in conjunction with, realize cation dye chromophil.Contain carboxylic acid The diamine monomer and phosphorous-containing monomers of group have biggish space steric effect, reduce the crystallinity of polymer, increase it without fixed Type form reduces time and material cost during stock-dye, bis- (3- aminophenyl) phenylphosphine oxides of phosphorous-containing monomers Effective raising flame-retardant fiber performance is added.

Further, the viscosity of modified poly (m-phenylene isophthalmide) spinning dope is 40~70Pas, to guarantee height Molecule performance meets spinning requirement.

Further, during preparing modified poly (m-phenylene isophthalmide) spinning dope, first by MPD, DABAS and BAPPO mixing, is cooled to low temperature for reaction system after mixing evenly, prepares for the polymerization reaction of next step；It will IPC is added in reaction system, and reaction takes place in adition process, because can release in entire polymerization process a large amount of Heat, therefore early period turns down temperature, while IPC being added in two times, prevents from being added at one time the heat release of IPC whole system too More, system temperature does not meet reaction condition, and polymerization reaction can not be normally carried out；In being added in the system after polymerization reaction again And agent limits neutralizer and was added so that final solution has the neutrallty condition that preparation easily contaminates modified meta-aramid precursor The temperature of system C in journey prevents that side reaction can occur in adition process.

[specific embodiment]

Below with reference to specific steps, the invention will be described in further detail.The technical solution adopted by the present invention is isophthalic Diamines (MPD), m-phthaloyl chloride (IPC), 3,5- diaminobenzoic acid sodium (DABAS) and the oxidation of bis- (3- aminophenyl) phenyl Low-temperature polycondensation obtains modified poly (m-phenylene isophthalmide) spinning dope to phosphorus (BAPPO) in organic solvent, then by wet Method spinning, deionized water are repeatedly washed, drying, and thermal finalization, which is made, easily contaminates modified meta-aramid.

Described one kind easily dye meta-aramid chemical structural formula are as follows:

Wherein: 5≤X≤10,1≤Y≤5,85≤Z≤94.

This it is easy dye meta-aramid preparation process the following steps are included:

Step 1, under room temperature, nitrogen dry environment, in organic solvent according to molar ratio (85~94): (1~5): (5 ~10) MPD, DABAS and BAPPO is added, after the dissolution of revolving speed 200~2000r/min mechanical stirring, system is cooled to -20 ~-10 DEG C, form diamine solution；The organic solvent is N,N-dimethylformamide (DMF), DMAC N,N' dimethyl acetamide (DMAc), one or more of N-Methyl pyrrolidone (NMP) and dimethyl sulfoxide (DMSO)；

Step 2, IPC is added in two portions in diamine solution within 30min, the IPC of addition and MPD, DABAS of addition and The molar ratio of BAPPO total amount be (1.002~1.01): 1, for the first time be added IPC Zhan be always added IPC mass 0.3~ 0.7%, remaining IPC are added for the second time, and in IPC adition process, control reaction temperature is -20~-10 DEG C.React 10-30min Whole system is warming up to -1~3 DEG C, preferably 0 DEG C afterwards, judges that polymerization reaction is completed after rod climbing phenomenon occurs in reaction system； Neutralizer calcium hydroxide or liquefied ammonia are added in the reaction system, by the pH of whole system to adjusting to 6-8, neutralization reaction process The middle temperature that need to guarantee whole system is no more than 80 DEG C, to prevent the generation of side reaction；Between obtained modification is poly- after neutralization reaction Phenyl-diformyl m-phenylene diamine (MPD) polymer solution, the viscosity of modified poly (m-phenylene isophthalmide) spinning dope obtained is 40~ 70Pa·s。

Step 3, easily dye is made by wet spinning in modified poly polymer solution obtained Modified meta-aramid precursor, wherein the technological parameter of wet spinning refers to patent CN200910259778, will easily contaminate between being modified Inflammable modified meta-aramid is made in drying, thermal finalization after position aramid fiber precursor washs repeatedly；The drying temperature is 120~180 DEG C, It is dried to fiber moisture < 5%, heat setting temperature is 200~400 DEG C, and hot-stretch multiple is 1.5~4 times, thermal finalization fiber To stable molding.

The present invention will be further described combined with specific embodiments below: