CN1911974B - Synthesis method of acrylonitrile and chloroethylene copolymer - Google Patents
Synthesis method of acrylonitrile and chloroethylene copolymer Download PDFInfo
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Abstract
The synthesis process of acrylonitrile-vinyl chloride copolymer relates to the preparation of no-additive fireproof acrylon resin. The synthesis process of acrylonitrile-vinyl chloride copolymer includes throwing vinyl chloride monomer into reaction kettle, throwing the solution compounded with sodium dodecyl sulfate, OP-10, initiator, anhydrous sodium acetate, glacial acetic acid and EDTA into reaction kettle, heating to 30-60 deg.c, adding solution compounded with acrylonitrile monomer, initiator, sodium dodecyl sulfate and water with two metering pumps, so as to react until the pressure is lowered to 0.2 MPa; discharging to obtain white emulsion; demulsifying the emulsion with saturated sodium chloride solution to obtain paste; water washing in a centrifuge, dewatering and drying to obtain fireproof acrylon resin. The copolymer product has raised stability and conversion rate.
Description
Technical field
The present invention relates to a kind of preparation method of non-additive flame retardant acrylic fibers resin.
Background technology
Abroad, a lot of industries all have the quite fire-retardant requirement of strictness with the field to fabric, fabric lining etc., like the interior trim in public place, hotel, hotel etc., carpet, curtain, wall cloth etc., must meet corresponding legal fire-protection standard; The protective clothing of special trades such as baby's nightwear, Fr also must adopt fire retardant material.And at home; The industry standard of this respect, decree rules are sound as yet, and along with improving constantly of development and national economy and living standards of the people, people recognize that gradually fiber is prevented fires, fire-retardant importance; Therefore, the exploitation of fire-retardant fibre has very big realistic meaning and marketable value.
Acrylic fibers are widely used in aspects such as clothing, imitative wool fabric as a kind of filamentary material commonly used.At present, the fire-retardant methods of adding fire retardant that adopt for acrylic fibers solve more.Adopt and add the acrylic fiber that fire retardant (halogen, phosphorus are material etc.) is produced, flameproof effect is relatively poor, and fire retardant is easy to run off in processing and use, and the fire resistance property of fiber is reduced gradually; Simultaneously, the most of fire retardant that uses at present can produce very big pollution to environment, is unfavorable for Sustainable development; And the affiliation that adds of additive produces detrimentally affect to mechanical performance indexs such as the tensile strength of acrylic fiber, elongation at breaks.
A kind of desirable approach that solves the fire-retardant problem of acrylic fibers is the synthetic acrylic fibers resin that has flame retardant effect itself.Research both at home and abroad is more, and the non-additive flame retardant acrylic fibers resin of suitability for industrialized production is arranged is vinylidene chloride-acrylonitrile compolymer resin.But adopt vinylidene chloride as after the fire-retardant monomer introducing acrylonitrile polymerization, the multipolymer spinning that obtains, its feel is hard partially, and fiber is not so good as common acrylic fiber aspect kindliness.
The vinyl chloride monomer structure is similar with vinylidene chloride; But has only a chlorine atom on the vinylchlorid molecular chain; Its generation sterically hindered less than vinylidene chloride; Therefore adopt vinylchlorid as after the fire-retardant monomer introducing acrylonitrile polymerization, after the spinning of resulting flame-retardant acrylic fibre resin, aspect kindliness, be superior to vinylidene chloride-acrylonitrile copolymer.
But the reactive behavior of vinylchlorid and vinyl cyanide differs greatly, and polymerization of acrylonitrile speed is much larger than the speed of response of vinylchlorid, so two kinds of monomeric dosing methods, becomes the important factor of impact polymer product composition, stability and transformation efficiency.
Summary of the invention
The objective of the invention is to seek the compound method of the multipolymer of a kind of vinyl cyanide and vinylchlorid, adopt progressively synthetic uniform vinylchlorid and the acrylonitrile copolymer formed of method, to improve the stability and the transformation efficiency of polymeric articles.
According to plan provided by the present invention, in the compound method of the multipolymer of vinyl cyanide and vinylchlorid, main raw material and content are following:
Vinyl chloride monomer 100
Acrylonitrile monemer 120-200
Sodium lauryl sulphate 1-10
OP-10 1—5
Initiator 1-4
Sodium acetate, anhydrous 0.3-0.5
Glacial acetic acid min. 99.5 0.3-0.5
Ethylene dinitrilotetra-acetic acid 0.1
Unit is a weight part;
According to the above ratio, vinyl chloride monomer is dropped in the reaction kettle, with sodium lauryl sulphate, OP-10, initiator, sodium acetate, anhydrous, Glacial acetic acid min. 99.5, ethylene dinitrilotetra-acetic acid, be mixed with solution after, drop in the reaction kettle; Be warming up to 30-60 ℃, with two volume pumps respectively all uniform flow add the solution that acrylonitrile monemer and initiator, sodium lauryl sulphate and water are made into; After reaction was depressurized to 0.2MPa, discharging obtained white emulsion; Emulsion becomes body of paste after with the saturated nacl aqueous solution breakdown of emulsion, again in whizzer with clear water wash, dewater, drying, obtain the flame-retardant acrylic fibre resin.
Said initiator is one or more in Sodium Pyrosulfite, sodium sulfite anhy 96, ammonium persulphate or the Potassium Persulphate.
The flame-retardant acrylic fibre resin that polymerization obtains adopts acrylic fibers DMF wet spinning technology to carry out spinning, and the gained fiber is carried out tensile property and flame retardant properties test.
The present invention adopts the adding mode of different acrylonitrile monemers, synthesizing chloroethylene and acrylonitrile copolymer, i.e. single stage method, two-step approach and progressively method.Wherein, single stage method refers to that acrylonitrile monemer reacts with vinyl chloride monomer in the initial disposable adding reaction kettle of polyreaction; Two methods are meant that earlier a part of acrylonitrile monemer being added reaction kettle before the reaction beginning advances, and a part of in addition acrylonitrile monemer then carries out adding polymerization reaction kettle in the process in reaction; Progressively method is meant that acrylonitrile monemer is after the reaction beginning, and, uniform flow in adding reaction kettle progressively with acrylonitrile monemer are reacted the method that stable reaction is carried out with vinylchlorid.。
The invention has the advantages that: 1, employing compound method of the present invention makes the molecular weight of copolymer height, monomer conversion is higher; 2, progressively the advantage of method is that polymerisation conversion is high, and product is formed evenly, and progressively method is formed than process and product that two-step approach is more prone to control reaction; 3, entire reaction course is a may command through the speed of adding of regulating vinyl cyanide, and the composition of product also can be controlled through the dosing method of vinyl cyanide; 4, progressively the silk breaking tenacity spun of method synthetic multipolymer and elongation at break all than single stage method and the synthetic resulting copolymerization object height of two-step approach.5, compound method of the present invention has advantages such as simple to operate, with short production cycle, that cost is lower, is a kind of compound method that is easy to large-scale industrial production.
Embodiment
Embodiment one
With vinylchlorid 5000 grams, add in the polymerization reaction kettle sodium lauryl sulphate 100 grams, OP-1050 gram; Ammonium persulphate 5 grams, Sodium Pyrosulfite 40 grams, sodium acetate, anhydrous 25 grams, Glacial acetic acid min. 99.5 18 grams; Ethylene dinitrilotetra-acetic acid 5 gram, be mixed with solution after, drop in the reaction kettle water 23700 grams.After 20 minutes, be warming up to 45 ℃ with 220 rev/mins of stirrings.After reaching temperature of reaction, add vinyl cyanide 5000 grams and compounding agent solution (120 gram ammonium persulphates, 350 gram sodium lauryl sulphate, 4000 gram water) with the equal uniform flow of volume pump.After reaction was depressurized to 0.2MPa, discharging obtained white emulsion.Emulsion with the saturated nacl aqueous solution breakdown of emulsion after, washing, dehydration, drying obtain vinylchlorid and acrylonitrile copolymer.Polymericular weight 146224, MWD 1.834, reaction total conversion rate 79.54%.The 10 hours step-down time of reaction.Behind solvent spinning, resulting fibre breakage intensity 1.80CN/dtex, elongation at break 41.7%, limiting oxygen index(LOI) are 32.
Embodiment two
With vinylchlorid 5000 grams, add in the polymerization reaction kettle sodium lauryl sulphate 100 grams, OP-1050 gram; Ammonium persulphate 5 grams, Sodium Pyrosulfite 40 grams, sodium acetate, anhydrous 25 grams, Glacial acetic acid min. 99.5 18 grams; Ethylene dinitrilotetra-acetic acid 5 gram, be mixed with solution after, drop in the reaction kettle water 23700 grams.After 20 minutes, be warming up to 30 ℃ with 220 rev/mins of stirrings.After reaching temperature of reaction, add vinyl cyanide 5000 grams and compounding agent solution (120 gram ammonium persulphates, 350 gram sodium lauryl sulphate, 4000 gram water) with the equal uniform flow of volume pump.After reaction was depressurized to 0.2MPa, discharging obtained white emulsion.Emulsion with the saturated nacl aqueous solution breakdown of emulsion after, washing, dehydration, drying obtain vinylchlorid and acrylonitrile copolymer.Polymericular weight 155244, MWD 1.623, reaction total conversion rate 80.66%.The 16 hours step-down time of reaction.Behind solvent spinning, resulting fibre breakage intensity 2.13cN/dtex, elongation at break 40.6%, limiting oxygen index(LOI) are 31.
Embodiment three
With vinylchlorid 5000 grams, add in the polymerization reaction kettle sodium lauryl sulphate 100 grams, OP-1050 gram; Ammonium persulphate 5 grams, Sodium Pyrosulfite 50 grams, sodium acetate, anhydrous 25 grams, Glacial acetic acid min. 99.5 18 grams; Ethylene dinitrilotetra-acetic acid 5 gram, be mixed with solution after, drop in the reaction kettle water 23700 grams.After 20 minutes, be warming up to 60 ℃ with 220 rev/mins of stirrings.After reaching temperature of reaction, add vinyl cyanide 5000 grams and compounding agent solution (120 gram ammonium persulphates, 350 gram sodium lauryl sulphate, 4000 gram water) with the equal uniform flow of volume pump.After reaction was depressurized to 0.2MPa, discharging obtained white emulsion.Emulsion with the saturated nacl aqueous solution breakdown of emulsion after, washing, dehydration, drying obtain vinylchlorid and acrylonitrile copolymer.Polymericular weight 138186, MWD 1.998, reaction total conversion rate 78.27%.The 8 hours step-down time of reaction.Behind solvent spinning, resulting fibre breakage intensity 1.32cN/dtex, elongation at break 42.2%, limiting oxygen index(LOI) are 31.
Embodiment four
With vinylchlorid 5000 grams, add in the polymerization reaction kettle sodium lauryl sulphate 100 grams, OP-1050 gram; Ammonium persulphate 5 grams, Sodium Pyrosulfite 40 grams, sodium acetate, anhydrous 25 grams, Glacial acetic acid min. 99.5 18 grams; Ethylene dinitrilotetra-acetic acid 5 gram, be mixed with solution after, drop in the reaction kettle water 23700 grams.After 20 minutes, be warming up to 45 ℃ with 220 rev/mins of stirrings.After reaching temperature of reaction, add vinyl cyanide 3000 grams and compounding agent solution (120 gram ammonium persulphates, 350 gram sodium lauryl sulphate, 4000 gram water) with the equal uniform flow of volume pump.After reaction was depressurized to 0.2MPa, discharging obtained white emulsion.Emulsion with the saturated nacl aqueous solution breakdown of emulsion after, washing, dehydration, drying obtain vinylchlorid and acrylonitrile copolymer.Polymericular weight 158679, MWD 1.815, reaction total conversion rate 80.09%.The 9 hours step-down time of reaction.Behind solvent spinning, resulting fibre breakage intensity 1.82cN/dtex, elongation at break 40.9%, limiting oxygen index(LOI) are 33.
Embodiment five
With vinylchlorid 5000 grams, add in the polymerization reaction kettle sodium lauryl sulphate 100 grams, OP-1050 gram; Ammonium persulphate 5 grams, Sodium Pyrosulfite 40 grams, sodium acetate, anhydrous 25 grams, Glacial acetic acid min. 99.5 18 grams; Ethylene dinitrilotetra-acetic acid 5 gram, be mixed with solution after, drop in the reaction kettle water 23700 grams.After 20 minutes, be warming up to 45 ℃ with 220 rev/mins of stirrings.After reaching temperature of reaction, add vinyl cyanide 8000 grams and compounding agent solution (120 gram ammonium persulphates, 350 gram sodium lauryl sulphate, 4000 gram water) with the equal uniform flow of volume pump.After reaction was depressurized to 0.2MPa, discharging obtained white emulsion.Emulsion with the saturated nacl aqueous solution breakdown of emulsion after, washing, dehydration, drying obtain vinylchlorid and acrylonitrile copolymer.Polymericular weight 130891, MWD 2.103, reaction total conversion rate 75.64%.The 15 hours step-down time of reaction.Behind solvent spinning, resulting fibre breakage intensity 1.73cN/dtex, elongation at break 42.0%, limiting oxygen index(LOI) are 29.
Comparative Examples one
With vinylchlorid 5000 grams, vinyl cyanide 5000 grams add in the polymerization reaction kettle, sodium lauryl sulphate 100 grams; The OP-1050 gram, ammonium persulphate 5 grams, Sodium Pyrosulfite 40 grams; Sodium acetate, anhydrous 25 grams, Glacial acetic acid min. 99.5 18 grams, ethylene dinitrilotetra-acetic acid 5 grams; After being mixed with solution, drop in the reaction kettle water 23700 grams.After 20 minutes, be warming up to 45 ℃ with 220 rev/mins of stirrings.After reaching temperature of reaction, with the equal uniform flow adding assistant of volume pump solution (120 gram ammonium persulphates, 350 gram sodium lauryl sulphate, 4000 gram water).After reaction was depressurized to 0.2MPa, discharging obtained white emulsion.Emulsion with the saturated nacl aqueous solution breakdown of emulsion after, washing, dehydration, drying obtain vinylchlorid and acrylonitrile copolymer.Polymericular weight 99960, MWD 3.140, reaction total conversion rate 64.89%.Behind solvent spinning, resulting fibre breakage intensity 1.02cN/dtex, elongation at break 39.3%, limiting oxygen index(LOI) are 32.
Comparative Examples two
With vinylchlorid 5000 grams, vinyl cyanide 1000 grams add in the polymerization reaction kettle, sodium lauryl sulphate 100 grams; The OP-1050 gram, ammonium persulphate 5 grams, Sodium Pyrosulfite 40 grams; Sodium acetate, anhydrous 25 grams, Glacial acetic acid min. 99.5 18 grams, ethylene dinitrilotetra-acetic acid 5 grams; After being mixed with solution, drop in the reaction kettle water 23700 grams.After 20 minutes, be warming up to 45 ℃ with 220 rev/mins of stirrings.After reaching temperature of reaction, add vinyl cyanide 4000 grams and compounding agent solution (120 gram ammonium persulphates, 350 gram sodium lauryl sulphate, 4000 gram water) with the equal uniform flow of volume pump.After reaction was depressurized to 0.2MPa, discharging obtained white emulsion.Emulsion with the saturated nacl aqueous solution breakdown of emulsion after, washing, dehydration, drying obtain vinylchlorid and acrylonitrile copolymer.Polymericular weight 133207, MWD 2.217, reaction total conversion rate 67.96%.Behind solvent spinning, resulting fibre breakage intensity 1.28cN/dtex, elongation at break 39.1%, limiting oxygen index(LOI) 30.
Claims (2)
1. the progressively method compound method of the multipolymer of vinyl cyanide and vinylchlorid, its main raw material and content are following:
Vinyl chloride monomer 100
Acrylonitrile monemer 120-200
Sodium lauryl sulphate 1-10
OP-10 1-5
Initiator 1-4
Sodium acetate, anhydrous 0.3-0.5
Glacial acetic acid min. 99.5 0.3-0.5
Ethylene dinitrilotetra-acetic acid 0.1
Unit is a weight part;
According to the above ratio, vinyl chloride monomer is dropped in the reaction kettle, with sodium lauryl sulphate, OP-10, initiator, sodium acetate, anhydrous, Glacial acetic acid min. 99.5, ethylene dinitrilotetra-acetic acid, be mixed with solution after, drop in the reaction kettle; Be warming up to 30-60 ℃, with two volume pumps respectively all uniform flow add the solution that acrylonitrile monemer and initiator, sodium lauryl sulphate and water are made into; After reaction was depressurized to 0.2MPa, discharging obtained white emulsion; Emulsion becomes body of paste after with the saturated nacl aqueous solution breakdown of emulsion, again in whizzer with clear water wash, dewater, drying, obtain the flame-retardant acrylic fibre resin;
Said initiator is one or more in Sodium Pyrosulfite or the Potassium Persulphate.
2. the compound method of the multipolymer of vinyl cyanide and vinylchlorid according to claim 1 is characterized in that, the flame-retardant acrylic fibre resin that polymerization obtains adopts acrylic fibers DMF wet spinning technology to carry out spinning, and the gained fiber is carried out tensile property test with flame retardant properties.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2006100881029A CN1911974B (en) | 2006-06-26 | 2006-06-26 | Synthesis method of acrylonitrile and chloroethylene copolymer |
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| CN2006100881029A CN1911974B (en) | 2006-06-26 | 2006-06-26 | Synthesis method of acrylonitrile and chloroethylene copolymer |
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| CN1911974B true CN1911974B (en) | 2012-03-21 |
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| CN109537099A (en) * | 2018-12-04 | 2019-03-29 | 宿迁广和新材料有限公司 | A kind of multicomponent polymeric blending fire retardant precursor and preparation method thereof |
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