CN1132862C - :Modacrylic copolymer composition - Google Patents
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- CN1132862C CN1132862C CN 00805536 CN00805536A CN1132862C CN 1132862 C CN1132862 C CN 1132862C CN 00805536 CN00805536 CN 00805536 CN 00805536 A CN00805536 A CN 00805536A CN 1132862 C CN1132862 C CN 1132862C
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Abstract
The present invention relates to a modacrylic copolymer composition comprising acrylonitrile, vinylidene chloride, vinyl acetate, and at least one ionic comonomer. In one embodiment, the modacrylic copolymer composition comprises from about 45 to about 60% acrylonitrile, from about 35 to about 50% vinylidene chloride, from about 0.5 to about 5% vinyl acetate, and up to about 2% of a salt of p-sulfophenyl methallyl ether by weight of the total composition. The copolymer composition of the present invention provides acceptable color while having acceptable flame resistance.
Description
The present invention relates to improve acrylic copolymer composition and prepare the method that improves acrylic copolymer composition.The invention still further relates to of the conversion of improvement acrylic copolymer composition to fiber with acceptable fire behaviour and/or carpet.
Background of the present invention
Various have some required physical properties such as high strength, high wet fusing point and inotropic polyacrylonitrile fibres of good resistance have at high temperature been spun.These character of polyacrylonitrile fibre have promoted their application in many commerce and textile field.But,, cause the purposes of these fibers to be restricted because polyacrylonitrile fibre does not have enough flame retardant propertiess.
Make great efforts to improve aspect the flame retardant properties of acryl fibre, vinyl cyanide and some monomer such as vinylchlorid and vinylidene chloride have been carried out copolymerization.The improvement degree of flame retardant properties changes with type and the quantity with the properties-correcting agent of acrylonitrile compolymer.Have the properties-correcting agent that enough flame retardant propertiess are provided but be difficult to provide, also have acceptable fiber properties such as acceptable color, high anti-contracility, high strength, high wet fusing point and acceptable chromatic acryl fibre simultaneously.Run into these difficulties, part is because the difficulty of solubilising vinylchlorid or vinylidene chloride.
Developed the mixture of the various acrylonitrile copolymers that comprise vinyl cyanide and vinylidene chloride.For example, be incorporated into this paper United States Patent (USP) 2,769 as a reference, 793 have described and have a kind ofly contained 85% or the acrylonitrile copolymer mixture of more acrylonitrile polymers, this mixture can comprise various monomer components, as vinylchlorid, vinyl-acetic ester, vinylidene chloride etc.This mixture also can contain the monomer of drawing dyestuff.Be incorporated into this paper United States Patent (USP) 3,828 as a reference, but 014 relates to the formed fiber of multipolymer that is belonged to unsaturated monomer by the monoene of vinyl cyanide and one or more copolymerization.But the acrylonitrile mixture that these patents are described can not have enough fibrous properties, fiber process, flame retardant resistance and dyeability simultaneously.
Fiber industry constantly makes great efforts not only have flame retardant properties to provide, and also has the fiber of improved fiber light fastness, fiber dyeing and fiber color.Be incorporated into this paper United States Patent (USP) as a reference and described a kind of anti-flaming acrylic fiber that contains vinyl cyanide, vinylidene chloride and vinyl phosphonate for 3,824, No. 222.Be incorporated into this paper United States Patent (USP) as a reference and relate to a kind of non-flammable vinyl cyanide-vinylidene chloride copolymer fibre for 3,974, No. 130, this fiber comprises the comonomer that dyestuff is had special avidity.But, be called as acrylic acid these fiber compositions of improvement and contain a large amount of vinylidene chloride (being that concentration surpasses 25% weight).The prior art composition that contains vinylidene chloride has bad fiber properties and the relatively poor shortcoming of color.When the vinylidene chloride of the necessary amount that the formation fiber is required makes fiber have resistivity against fire, can make fiber have several unwelcome characteristics.
When vinylidene chloride content surpasses 25% weight of copolymer compositions, because bad flame retardant resistance or bad basic multipolymer whiteness, thereby can not obtain gratifying prior art multipolymer.Vinylidene chloride also has disadvantageous effect to the light fastness of fiber and other characteristic such as ultra-violet resistance.Because 1, the low solubility of 1-Ethylene Dichloride, the vinylidene chloride of high density makes processing more complicated like this in the prior art multipolymer, and the fiber that causes producing has unacceptable character such as insufficient fibrous texture (as tensile property), light fastness and dyeability.
But the binding substances that the gratifying improvement acrylic acid mixture of a class commercial production is bromine ethene and vinylidene chloride and other comonomer.A kind of this class mixture contains 61.45% vinyl cyanide, the 1.5% pair of sulfophenyl methallyl ethers sodium, 12.5% bromine ethene, 23.9%1,1-Ethylene Dichloride and 0.65% vinylbenzene.The chemical abstracts of this copolymer compositions is numbered CAS#31532-91-9, and it is the multipolymer of a kind of vinyl cyanide-bromine ethene-vinylidene chloride.
But the operability of bromine ethene descends recently.
Therefore, need a kind of modacrylic fiber composition so that fiber has the binding characteristic of ideal fibrous texture, light fastness, color and flame retardant resistance.
And, in various other industry, also need fire-retardant polymeric material in order to form various products, these products can not run into monomer and the complicated problem of copolymer compositions inherent color earlier.
The present invention's general introduction
The present invention relates to contain the monomeric improvement acrylic copolymer composition of vinyl cyanide, vinylidene chloride, vinyl-acetic ester and at least a ionic copolymerization.Described improvement acrylic copolymer composition contains the vinyl-acetic ester of the vinyl cyanide that accounts for the about 45%-of total composition weight about 60%, the vinylidene chloride of about 35%-about 50%, about 0.5%-about 5% and the salt to the sulfophenyl methallyl ethers of 0-about 2%.
Copolymer compositions of the present invention provides acceptable fibrous property about intensity and color, has acceptable to catching fire and pyrogenic resistivity simultaneously.The color of the compacting polymkeric substance that defines in the embodiment of mixture approximates the color of prior art bromine ethene commodity mixture CAS#31532-91-9 noted earlier greatly for making an appointment with-7 to making an appointment with-11.
Can utilize copolymer compositions of the present invention with various forms (comprising formed article), and can make its fiber that forms molecular orientation, line, bristlelike monofilament, monofilament etc., also can make it form other form, for example film, matrix material, laminate, powder, particle, ball shape, solution, dispersion, gel, mashed prod etc.
The present invention describes in detail
Term used herein improvement vinylformic acid be contain be bonded to wherein greater than about 45% but less than the monomeric multipolymer of the acrylonitrile compolymer of about 85% weight.
The present invention relates to contain the monomeric improvement acrylic copolymer composition of vinyl cyanide, vinylidene chloride, vinyl-acetic ester and at least a ionic copolymerization.Described improvement acrylic copolymer composition contains 1 of the vinyl cyanide that accounts for the about 45%-of total composition weight about 60%, about 35%-about 50%, the vinyl-acetic ester of 1-Ethylene Dichloride, about 0.5%-about 5%, and up to about the monomeric salt of 2% ionic copolymerization, preferably to sulfophenyl methallyl ethers sodium.Usually comparatively favourable at least about a small amount of ionic copolymerization monomer of 0.1% weight for dyeability, and help to obtain more intensive fibrous texture.
Preferred compositions contains the vinyl-acetic ester of the vinyl cyanide that accounts for the about 49%-of total composition weight about 59%, the vinylidene chloride of about 39%-about 49%, about 0.5%-about 2.5% and the salt to the sulfophenyl methallyl ethers of about 0.1%-about 1.5%.Preferred ionic copolymerization monomer is sodium salt to the sulfophenyl first for the salt of allyl ether.
Another kind of preferred compositions can contain the vinyl-acetic ester of the vinyl cyanide that accounts for the about 50%-of total composition weight about 57%, the vinylidene chloride of about 41%-about 48%, about 0.5%-about 1.5% and about 0.5%-about 1.5% to the salt of sulfophenyl first for allyl ether.
Another kind of preferred compositions can contain the vinyl-acetic ester of the vinyl cyanide that accounts for the about 49%-of total composition weight about 53%, the vinylidene chloride of about 45%-about 49%, about 0.8%-about 1.2% and about 0.8%-about 1.2% to the salt of sulfophenyl first for allyl ether.
An example of preferred compositions can be every kind of component be respectively vinyl cyanide 52.9% weight, to the sulfophenyl first for allyl ether sodium 1.0% weight, vinylidene chloride 45.1% weight, vinyl-acetic ester 1.0% weight, add or deduct about 0.1% weight.
Another example of preferred compositions can be every kind of component be respectively vinyl cyanide 50.2% weight, to the sulfophenyl first for allyl ether sodium 1.0% weight, 1,1-Ethylene Dichloride 47.8% weight, vinyl-acetic ester 1.0% weight add or deduct about 0.1% weight.
The disclosure is relevant with the discovery of the new and improved acrylic copolymer composition that contains vinyl-acetic ester.Many embodiments in the claim scope demonstrate the chromatic number of-10% compacting polymkeric substance.This value is the result of defined standard testing among the embodiment, and it reflects the amount of unwanted redness in multipolymer.-10% test result is the same good with the color of the compacting polymkeric substance of the aforementioned prior art mixture that is called CAS#31532-91-9.Expect that the colour of the compacting polymkeric substance that copolymer compositions of the present invention can be realized is approximately-7% to approximately-15%, more preferably from about-7% to approximately-12%.
The color measurement result of-10% the compacting multipolymer of realizing with composition of the present invention is better than the color of the compacting multipolymer of commercially available prior art multipolymer, this prior art multipolymer contains 59.5% vinyl cyanide, 1% pair of sulfophenyl first for allyl ether sodium, 39%1,1-Ethylene Dichloride and 0.5% vinylbenzene are (hereinafter referred to as CAS#9010-76-8, be a kind of multipolymer of vinyl cyanide-vinylidene chloride).
The chemical structure of described multipolymer can be described with following formula:
Wherein be the vinyl-acetic ester of 108-05-4, CAS number the sulfophenyl first is existed with the weight fraction that v, x, y and z provide respectively for the vinylidene chloride of 75-34-4 for allyl ether sodium and CAS number for the vinyl cyanide of 107-13-1, CAS number CAS number for 1208-67-9.
Neutral modification vinyl comonomer, particularly vinyl-acetic ester of the present invention make the whiteness of basic copolymer compositions improve to have surpassed and contain greater than 25%1, the prior art composition of 1-Ethylene Dichloride, and also kept resistivity against fire and other desired characteristic simultaneously.
In improvement vinylformic acid, use 1% vinyl-acetic ester to make also that required activator and initiator content reduced by 30% in the reductionoxidation polymerization reaction.Minimizing activator and initiator content help to reduce the color development defective in the polyacrylonitrile.Referring to L.Patron and U.Bastianelli,
Appl.Polym.Symp.No. 25,105 (1974) and J.Kim, C.Park, Y.Park, B Min, T son, and J.Ryu,
J.of the Korean Fiber Soc., 34,49 (1997).But, do not see the difference of tangible color development functionality by the specific infrared absorption in the document owing to ketene-imine.
And, having passed through the resistivity against fire test procedure that is used for fire-Resistant Fabric and film that the NFPA of version in 1989 proposes by the fabric of making from the fiber of copolymer compositions of the present invention, it is also referred to as NFPA 701 test on a small scale.The resistivity against fire test procedure of the fire-spreading property that is used for fabric and film that proposes by Underwriters LaboratoriesInc. of version in 1997, i.e. Standard 214 Small-Flame Test have also been passed through by the fabric of making from the fiber of copolymer compositions of the present invention.
Term used herein " fire-Resistant Fabric " is meant the great majority that passed through NFPA 701 (1989) and/or Underwriters Laboratories Inc.Standard 214 resistivity against fires tests (1997), promptly greater than 80% fabric.
NFPA 701 (1989) and UL 214 (1997) resistivity against fire test have on a small scale been passed through by the fabric of making from the fiber of improvement acrylic copolymer of the present invention.The whiteness of the improvement acrylic copolymer of measuring by the color measurement of compacting polymkeric substance of the present invention is better than not containing the composition of vinyl-acetic ester.At last, the reductionoxidation polymerization reacting phase ratio when in the improvement acrylic copolymer, not adding vinyl-acetic ester, when adding 1% vinyl-acetic ester in the improvement acrylic copolymer, activator that the reductionoxidation polymerization reaction is required and initiator reduce 30%.
Except to the sulfophenyl methyl allyl ether sodium, other ionic copolymerization monomer also can be made acceptable fiber." ionic copolymerization monomer " used herein is a kind of ionic copolymerization monomer that adds one or more ionic functional groups in copolymer compositions.The ionic functional group can be used as dry up-take location.Typical ionic functional group comprises sulfonate, carbonate and sulphate moiety.The ionic copolymerization monomer makes the composition of generation have required basic dyeing and copolymer structure, this texture improvement the post-treatment of multipolymer, as spinning.The ionic copolymerization monomer that preferably contains sulfonate, it is also referred to as " sulfonate ion comonomer ".
Sulfonate ion comonomer of the present invention can be represented with the band sulfonate of following formula (II) or the vinyl monomer of sulfonic acid:
Wherein A is typically methyl for preferably having the aromatics or the aliphatics substituting group of about 1-9 carbon atom; B is hydrogen or the aliphatics substituting group that preferably has about 1-9 carbon atom on vinyl monomer; M
+Represent the suitable counter ion of sulfonate groups, as alkali metal cation, alkaline earth metal cation, ammonium or hydronium(ion) positively charged ion.Aliphatics and aromatic group can not be substituted, can be by various components such as replacements such as halogen atom, organic group yet.The preferred aliphat group is a methyl.Preferred aromatic group is phenyl or phenyl ether group.
Suitable sulfonate ion comonomer comprises allylsulfonate, methallyl sulfonate, styrene sulfonate, to salt or the sulfonic acid of sulfophenyl first for allyl ether, 2-methyl-2-acrylamido propane sulfonate, acrylamido tertiary butyl sulfonic acid, or its mixture.Counter ion are generally sodium, although other basic metal, oxonium ion and ammonium also are suitable.Used herein term ionic copolymerization monomeric " salt " comprises the form of acid.The monomeric mixture of two or more ionic copolymerizations also is suitable.
Multipolymer of the present invention can prepare by any polymerization process, as the polymerization process of letex polymerization in water-bearing media or aqueous dispersion.Anion surfactant can be used in combination with a spot of nonionogenic tenside commonly used.Examples of anionic surfactants has, for example soap, vitriol, sulfonate and phosphoric acid salt.Under the situation of solution polymerization process, the preferred solvent with relatively little chain transfer constant, particularly preferred example such as ethylene carbonate, methyl-sulphoxide, N,N-dimethylacetamide or N, the dinethylformamide of using.Only otherwise hinder the uniform dissolution and the polymerizability of multipolymer, these solvents as polymerization reaction medium can contain a spot of water or other organic solvent.
Adopt the catalyzer of common radical polymerization initiator as polyreaction.The example of initiators for polymerization has, for example persulphate such as ammonium persulphate, Sodium Persulfate or Potassium Persulphate, the binding substances of persulphate and hydrosulphite such as sodium bisulfite or ammonium bisulfite, azo-compound is as 2,2 '-azo two (2, the 4-methyl pentane nitrile) and 2,2 '-Diisopropyl azodicarboxylate, superoxide such as di, t-butylperoxy pivarate and lauroyl peroxide, and the binding substances of superoxide such as hydrogen peroxide and organic reducing agent such as L-xitix.According to polymerisation process they are suitably selected.
In one embodiment of the invention, prepare the acrylic fiber copolymer precursor by the polymerization process with continuous free-radical oxidn reduction aqueous dispersion, wherein water is external phase, and initiator is water miscible.Redox system is made up of persulphate (oxygenant and initiator are sometimes referred to as " catalyzer "), sulfurous gas or hydrosulphite (reductive agent is sometimes referred to as " activator ") and iron (real redox catalyst).Can use the salt of described initiator and activator.Typical salt comprises ammonium, sodium or potassium.
Advantageously, with substantially the same but do not contain the required initiator of the composition of vinyl-acetic ester and the quantity of activator is compared, when introducing the vinyl-acetic ester of 1% weight, obtained similar result with activator with the initiator that reduces 30% at most.For example, for realizing about 75% the transformation efficiency of monomer to multipolymer, requirement only has based on monomer weight for the Sodium Persulfate initiator of 0.3-0.4% weight and only is the ammonium bisulfite activator of about 0.8% weight of 0.6-.This is equivalent at given reaction conditions, i.e. listed concentration of iron, water-content, temperature and every kilogram of monomer need about 0.17 mole initiator and the about 0.8 mole activator of about 0.6-of about 0.12-under the residence time among the embodiment 10 and 11.
With its with above-mentioned redox system, be used for the free radical that vinyl polymerization reacts not as producing with persulfate initiator, peroxide initiator or azo initiator.
Can adopt common wet spinning and dry-spinning method by copolymer fiber of the present invention, preferred especially wet spinning.Can use the solvent that is generally used for acrylonitrile polymer as the solvent for preparing spinning solution, as acetonitrile, acetone, N,N-dimethylacetamide, N, dinethylformamide and methyl-sulphoxide.Because multipolymer is by uniform dissolution, thus preferred N, dinethylformamide, N,N-dimethylacetamide and methyl-sulphoxide, preferred especially N,N-dimethylacetamide.Spinning solution or the reaction mixture that is obtained by solution polymerization and be used as spinning solution can contain additive when needed, for example stablizer such as pigment, organic zinc compound or organic reducing agent, improve reagent such as the titanium compound or the aluminum compound of feel, fire retardant such as antimony compounds, tin compound or bromine compounds.The concentration of multipolymer can be 15-40% weight in the spinning solution.Wet spinning is normally carried out according to the following steps: spinning solution is squeezed in the aqueous solution of 10-80% weight of solvent forming long filament, elongate filaments washes with water and dry.If desired, the long filament that obtains further can be stretched and thermal treatment.
In one embodiment of the invention, can form modacrylic fiber with the modacrylic fiber copolymer precursor that obtains thus, comprise dry-spinning and wet spinning by the whole bag of tricks, as those at United States Patent (USP) 3,088,188,3,193,603,3,253,880,3,402,235,3,426,104,3,507,823,3,867,499,3,932,577,4,067,948,4,294,884,4,447,384,4,873,142 and 5, the method that proposes in 496,510 all is incorporated into this paper as a reference with every kind of method.
The physical properties of improvement acrylic copolymer composition of the present invention can be used in the various application said composition.For example, described multipolymer comprises polar aprotic solvent such as N,N-dimethylacetamide, N at all kinds of SOLVENTS, dinethylformamide, methyl-sulphoxide etc., and in the aqueous solution such as zinc chloride (65%), Sodium Thiocyanate 99 (55%) etc., be soluble.
Improvement acrylic copolymer composition of the present invention has other ideal physical properties, comprises and other fiber, comprises the miscibility of acrylic fiber and modacrylic fiber.
In one embodiment of the invention, in spinning bath, make described copolymer compositions form fiber by wet spinning.Spin processes is that this field is known, referring to for example United States Patent (USP) 4,067,948 and 3,867,499, their disclosure is attached to this paper as a reference.Solvent in the spinning bath is usually with to dissolve the solvent phase of multipolymer same before the spinning.Also can comprise water in the spinning bath, that part of spinning bath comprises residuum usually.Be used for suitable organic spin solvent of the present invention and comprise N,N-dimethylacetamide, N, dinethylformamide, methyl-sulphoxide and ethylene carbonate.Suitable inorganic solvent comprises moisture Sodium Thiocyanate 99.Preferably used solvent is a N,N-dimethylacetamide in spin processes of the present invention.
Can carry out spinneret draft to spun long filament.Spinneret draft is and the speed of the contacted first group of draw roll of the long filament that the leaves spinning jet speed divided by the copolymer solution by spinning jet it to be controlled at 0.2-1.0, preferred 0.4-0.6.Under lower spinneret draft, long filament can be difficult to processing, and under higher spinneret draft, the long filament pore size is tending towards increasing.
Afterwards, to the stretching of wetting of described long filament.By described long filament being transported to second group of high speed roller, and the wet long filament that stretches provides the wet stretching of the about 8X of about 2X-.The temperature of using in wet drawing process can be from the second-order transition temperature of about described multipolymer to the wet melting temperatur that is lower than described multipolymer.
The wet melting temperatur that it is desirable to described multipolymer is preferably greater than about 130 ℃ greater than about 120 ℃, and to promote aftertreatment, promptly steam heat is handled.Measure wet melting temperatur by different scanning calorimetries, in the method described polymkeric substance and water are placed in the pressurized vessel, in a temperature range, measure caloric receptivity.Specific thermal change is represented wet melting temperatur.This is known in this area, and be standard testing, it is at Polymer Bulletin, 11, Bruce G.Frushour among the 375-382 (1984), " melting property of polyacrylonitrile multipolymer " (" MeltingBehavior of Polyacrylonitrile Copolymers) " in complete description is arranged.
Can before final the use, handle by the fiber that aforesaid method is produced by " at line relaxation (in-line relaxabion) " or batch heat.Realize by the following method in line relaxation: under 80 ℃ of temperature long filament is input to hot water bath usually, the solvent of steam or heating and water-bath are so that its boiling and pull out long filament with the contraction that takes place of compensation with lower speed in bath.Warming mill by routine or add warm air and make long filament drying after lax, these long filaments are suitable for using at this point, or do not need use through the staple fibre of batch heat process after being converted into.
The fiber that is formed by multipolymer of the present invention has the required physical properties that combine better than other copolymer fibre, comprises improved fibrous texture, flame retardant resistance, whiteness, dyeability, light fastness, wet fusing point etc.
Can comprise that the form of molding uses copolymer compositions of the present invention with various forms, they can be used to form the fiber of molecular orientation, i.e. line, bristlelike monofilament, monofilament etc.Also can make described multipolymer form other form such as film, matrix material, laminate, powder, particle, ball shape, solution, dispersion, gel, mashed prod etc. with purified form or with other additive blended form.
Copolymer compositions of the present invention and fiber are further defined by following illustrative embodiment.
Embodiment 1-5
Preparation improvement acrylate copolymer of the present invention in embodiment 3 and 4.As a comparison, also used and contained vinyl cyanide (AN), vinylidene chloride (VCl
2) and cinnamic commercially available improvement vinylformic acid, with its embodiment 1 and 5 in contrast.In order to contrast, preparation does not contain vinyl-acetic ester (VA) or cinnamic improvement vinylformic acid in embodiment 2 equally.The composition of described improvement acrylate copolymer is as shown in table 1.
The composition of multipolymer among the table 1 embodiment 1-5
Embodiment %AN %VA% SPME% VCl
2% vinylbenzene
1 59.50 --- 1.00 39.00 0.50
2 58.00 --- 1.00 41.00 ---
3 50.16 1.00 1.00 47.84 ---
4 52.89 1.00 1.00 45.11 ---
5 59.50 --- 1.00 39.00 0.50
Described multipolymer is made fiber product, be made into the forest green fabric then, by industrial standards NFPA 701 (1989) that is used for fabric and UL 214 (1997) small-scale resistivity against fire tests these fabrics are tested afterwards.The improvement acrylic copolymer made the method for fiber and be well known in the art the method that fiber is made fabric.The resistivity against fire data that obtain are as follows: the average burning of embodiment 1 is 5.1 inches, not by test; The average burning of embodiment 2 is 4.5 inches, not by test; The average burning of embodiment 3 is 3.6 inches, has passed through test; The average burning of embodiment 4 is 3.65 inches, has passed through test; The average burning of embodiment 5 is 3.9 inches, has passed through test.
Embodiment 2 is not for containing the comparative examples of neutral modification comonomer, not by test.Embodiment 1 and 5 has the blended result for containing cinnamic embodiment.The fabric of embodiment 3 and 4 for being made by composition of the present invention passed through the resistivity against fire test.
Embodiment 6-9
Preparation improvement acrylate copolymer of the present invention in embodiment 6 and 7.In order to contrast, use among the embodiment 8 to contain vinylidene chloride and cinnamic commercially available improvement vinylformic acid, use the improvement vinylformic acid that contains vinylidene chloride and bromine ethene among the embodiment 9.The composition of described multipolymer is as shown in table 2.
Last row provide color (PPC) test data of compacting polymkeric substance.The color measurement result of embodiment 6 and 7 compacting polymkeric substance is respectively-9.82% and-10.32%, is better than-10.43% the result who contains vinyl cyanide-bromine ethene-vinylidene chloride multipolymer (CAS#31532-91-9) composition among the embodiment 9 as a comparison.
The test result of embodiment 8 as a comparison is-19.23%.Compare with the color of other specimen, this is an obvious relatively poor color.
The composition of multipolymer among the table 2 embodiment 6-9
Embodiment %AN %VBr %VA %SPME %VCl
2% vinylbenzene %PPC
6 52.89 --- 1.00 1.00 45.11 --- -9.82
7 50.16 --- 1.00 1.00 47.84 --- -10.32
8 59.50 --- --- 1.00 39.00 0.50 -19.23
9 61.45 12.50 --- 1.50 23.90 0.65 -10.43
The color of described compacting polymkeric substance is a standard testing, is known in this area, and it comprises the steps: the multipolymer of known weight is placed in the mould platform, and then 40, the pressure of 000psi was pressed into a disk with 30 seconds with it down.Measure the color of disk then.The color of compacting polymkeric substance is an observed value, and this value is that the pellet that polymkeric substance is suppressed is obtained at the reflectivity percentage ratio that the reflectivity percentage ratio under the 420nm deducts under 600nm in BYK-Gardner Colorsphere.The chromatic number of compacting polymkeric substance is negative more, the unfavorable Huang-redness of the color of described polymkeric substance.
Embodiment 10
The following process of using the continuous aqueous dispersion of ammonium counter ion redox.The tank reactor of one 7.0 liters continuously stirring (with two 45 ° of impellers that have 6 blades that rotating under the 600rpm) is maintained at about under 35 ℃ the temperature.In proportion several strands of incoming flows introducing reactors being made its mean residence time in reactor is 150 minutes.PH is remained near 3.5.The composition of combined feed total feed is as shown in table 3.
By adding ammonium persulphate (oxygenant and initiator, be sometimes referred to as " catalyzer "), ammonium bisulfite (reductive agent is sometimes referred to as " activator ") and the aqueous solution ferrous or iron (real redox catalyst) and sulfuric acid (being used to control pH) comes initiated polymerization.These conditions make that monomer is 74.9% weight to the transformation efficiency of multipolymer.Final copolymer consist of 47.91% vinylidene chloride, 1.03% to the vinyl cyanide of sulfophenyl first for allyl ether sodium, 0.98% vinyl-acetic ester and equal amount.Recognize that can be another kind of positively charged ion to the sulfophenyl first for the salt of allyl ether, i.e. ammonium, but it is reported as the sodium salt that is used for transparency.The color of the compacting polymkeric substance of described multipolymer is-9.57%.
Join the composition in the continuous stirred tank reactor among table 3 embodiment 10
Compound
Quantity
Unit
Acrylonitrile monemer 49.6 weight parts
Vinylidene chloride monomer 48.6 weight parts
Vinyl acetate monomer 0.9 weight part
To the sulfophenyl first for allyl ether sodium monomer 0.9 weight part
Water 200.0 weight parts
Ammonium persulphate (initiator) 0.33 % is based on monomer
Ammonium bisulfite is as sulfurous gas (activator) 0.66 %, based on monomer
Iron (ferrous or iron) 1.6 ppm are based on monomer
The sulfuric acid trace
Embodiment 11
The following process of using the continuous aqueous dispersion of sodium counter ion redox.The tank reactor of one 7.0 liters continuously stirring (with two 45 ° of impellers with 6 blades that rotating under the 500rpm) is maintained at about under 35 ℃ the temperature.In proportion several strands of incoming flows introducing reactors being made its mean residence time is 150 minutes.PH is remained near 3.4.Feed composition is as shown in table 4.
By adding Sodium Persulfate (oxygenant and initiator, be sometimes referred to as " catalyzer "), sodium bisulfite (reductive agent is sometimes referred to as " activator ") and the aqueous solution ferrous or iron (real redox catalyst) and sulfuric acid (being used to control pH) comes initiated polymerization.These conditions make that monomer is 76.9% weight to the transformation efficiency of multipolymer.Final copolymer consist of 46.88% vinylidene chloride, 1.06% to the vinyl cyanide of sulfophenyl first for allyl ether sodium, 1.14% vinyl-acetic ester and equal amount.The color of the compacting polymkeric substance of multipolymer is-9.21%.
Join the composition in the continuous stirred tank reactor among table 4 embodiment 11
Compound
Quantity
Unit
Acrylonitrile monemer 51.6 umbers
Vinylidene chloride monomer 46.5 umbers
Vinyl acetate monomer 1.0 umbers
To the sulfophenyl first for allyl ether sodium monomer 0.9 umber
Water 200.0 umbers
Sodium Persulfate (initiator) 0.36 % is based on monomer
Sodium bisulfite is as sulfurous gas (activator) 0.72 %, based on monomer
Iron (ferrous or iron) 1.6 ppm are based on monomer
The sulfuric acid trace
The sodium bicarbonate trace
Above every kind of possible embodiment of the present invention is not listed in the description of specific embodiments of the present invention fully.It will be recognized by those skilled in the art and to make amendment to specific embodiments as herein described, and this will be within the scope of the present invention.
Claims (24)
1. improve acrylic copolymer for one kind, it comprises:
(a) vinyl cyanide of 49-59 weight percent;
(b) vinylidene chloride of 39-49 weight percent;
(c) vinyl-acetic ester of 0.5-5 weight percent; With
(d) the ionic copolymerization monomer of 0.1-2 weight percent.
2. the multipolymer of claim 1, wherein said multipolymer contains the vinyl cyanide of 50-57 weight percent, the vinylidene chloride of 41-48 weight percent, the vinyl-acetic ester of 0.5-1.5 weight percent and the ionic copolymerization monomer of 0.5-1.5 weight percent.
3. the multipolymer of claim 1, wherein said multipolymer contains the vinyl cyanide of 49-53 weight percent, the vinylidene chloride of 45-49 weight percent, the vinyl-acetic ester of 0.8-1.2 weight percent and the ionic copolymerization monomer of 0.8-1.2 weight percent.
4. the multipolymer of claim 1, wherein said multipolymer contains the vinyl cyanide of 52.8-53 weight percent, the vinylidene chloride of 45-45.2 weight percent, the vinyl-acetic ester of 0.9-1.1 weight percent and the ionic copolymerization monomer of 0.9-1.1 weight percent.
5. the multipolymer of claim 1, wherein said multipolymer contains the vinyl cyanide of 50.1-50.3 weight percent, the vinylidene chloride of 47.7-47.9 weight percent, the vinyl-acetic ester of 0.9-1.1 weight percent and the ionic copolymerization monomer of 0.9-1.1 weight percent.
6. the multipolymer of claim 1, wherein said ionic copolymerization monomer contains the sulfophenyl first for allyl ether or allylsulfonate, methallyl sulfonate, styrene sulfonate, to the salt of sulfophenyl first for allyl ether, 2-methyl-2-acrylamido propane sulfonate, acrylamide tertiary butyl sulfonic acid, or their mixture.
7. the multipolymer of claim 1, wherein said multipolymer is the form of film, matrix material, laminate, powder, particle, ball, solution, dispersion, gel or mashed prod.
8. the multipolymer of claim 1, the wet melting temperatur of wherein said multipolymer is greater than 130 ℃.
9. improve acrylic copolymer for one kind, it comprises:
(a) vinyl cyanide of 45-60 weight percent;
(b) vinylidene chloride of 35-50 weight percent;
(c) vinyl-acetic ester of 0.5-5 weight percent; With
(d) the 0-2 weight percent to the salt of sulfophenyl first for allyl ether.
10. the multipolymer of claim 9, wherein said multipolymer contain the vinyl-acetic ester of vinylidene chloride, 0.5-2.5 weight percent of vinyl cyanide, the 39-49 weight percent of 49-59 weight percent and 0.1-2 weight percent to the salt of sulfophenyl first for allyl ether.
11. the multipolymer of claim 9, wherein said multipolymer contain the vinyl-acetic ester of vinylidene chloride, 0.5-1.5 weight percent of vinyl cyanide, the 41-48 weight percent of 50-57 weight percent and 0.5-1.5 weight percent to the salt of sulfophenyl first for allyl ether.
12. the multipolymer of claim 9, wherein said multipolymer contain the vinyl-acetic ester of vinylidene chloride, 0.8-1.2 weight percent of vinyl cyanide, the 45-49 weight percent of 49-53 weight percent and 0.8-1.2 weight percent to the salt of sulfophenyl first for allyl ether.
13. the multipolymer of claim 9, wherein said multipolymer contain the vinyl-acetic ester of vinylidene chloride, 0.9-1.1 weight percent of vinyl cyanide, the 45-45.2 weight percent of 52.8-53 weight percent and 0.9-1.1 weight percent to the salt of sulfophenyl first for allyl ether.
14. the multipolymer of claim 9, wherein said multipolymer contain the vinyl-acetic ester of vinylidene chloride, 0.9-1.1 weight percent of vinyl cyanide, the 47.7-47.9 weight percent of 50.1-50.3 weight percent and 0.9-1.1 weight percent to the salt of sulfophenyl first for allyl ether.
15. the multipolymer of claim 9, the chromatic number of the compacting polymkeric substance of wherein said multipolymer is-7% to-15%.
16. the multipolymer of claim 9, the chromatic number of the compacting polymkeric substance of wherein said multipolymer is-7% to-12%.
17. the multipolymer of claim 9, the wet melting temperatur of wherein said multipolymer is greater than 120 ℃.
18. contain the fiber of improveing acrylic copolymer, wherein said improvement acrylic copolymer contains:
(a) vinyl cyanide of 49-59 weight percent;
(b) vinylidene chloride of 39-49 weight percent;
(c) vinyl-acetic ester of 0.5-5 weight percent; With
(d) the ionic copolymerization monomer of 0.1-2 weight percent.
19. the fiber of claim 18, wherein said improvement acrylic copolymer contain the vinyl-acetic ester of vinylidene chloride, 0.8-1.2 weight percent of vinyl cyanide, the 45-49 weight percent of 49-53 weight percent and 0.8-1.2 weight percent to the salt of sulfophenyl first for allyl ether.
20. the fiber of claim 18, wherein said fiber are the forms of fabric.
21. the fiber of claim 20, wherein said fabric are the mixtures of all kinds fiber.
22. the fiber of claim 20, wherein said fabric are flame-retardant textile.
23. method of producing the improvement acrylic copolymer, described method is included in to make in the polymerization process of free-radical oxidn reduction aqueous dispersion and contains vinyl cyanide, vinyl-acetic ester, ionic copolymerization monomer and 1, the monomer of 1-Ethylene Dichloride and at least a initiator, activator and redox catalyst reaction are to form multipolymer, the ionic copolymerization monomer of the vinyl cyanide that consists of the 45-60 weight percent of wherein said multipolymer, the vinyl-acetic ester of 0.5-5 weight percent, 0.01-2 weight percent and the vinylidene chloride of 35-50 weight percent.
24. the method for claim 23, wherein said initiator contains persulphate, and described activator contains one or more sulfurous gas or hydrosulphite, described catalyzer iron content or its salt.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/253,857 | 1999-02-02 | ||
| US09/253,857 US6154102A (en) | 1998-02-20 | 1999-02-22 | Controllable LC oscillator circuit |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1345341A CN1345341A (en) | 2002-04-17 |
| CN1132862C true CN1132862C (en) | 2003-12-31 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00805536 Expired - Fee Related CN1132862C (en) | 1999-02-02 | 2000-02-02 | :Modacrylic copolymer composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1300392C (en) * | 2002-04-29 | 2007-02-14 | 中国石油化工股份有限公司 | Fire resistant acrylonitrile copolymer fiber and manufacturing method thereof |
| CN1297697C (en) * | 2003-06-12 | 2007-01-31 | 中国石油化工股份有限公司 | Flameproof polyacrylonitrile fibre and method for preparing same |
| WO2016132877A1 (en) * | 2015-02-16 | 2016-08-25 | 株式会社カネカ | Method for producing acrylic fiber |
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| CN1345341A (en) | 2002-04-17 |
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