JP2003507503A - Melt-processable multipolymers comprising acrylonitrile monomers, halogenated monomers and olefinically unsaturated monomers, and methods for producing the multipolymers and their products - Google Patents

Abstract

  (57) [Summary] Numerous nitrile fibers or products can be prepared from a multipolymer of acrylonitrile monomers, halogenated monomers, and optionally olefinically unsaturated monomers, by thermal processing in the absence of a solvent. Nitrile multipolymers are thermostable and thermoplastic and produce excellent fibers and / or thermally processed products.

Description

Detailed Description of the Invention

[0001]

[Related application]

This application is filed on November 10, 1993, "Process for Making an Acryl."
08/150 named "Onitrile and Olefinically Unsaturated Polymer",
"Process for M, filed on February 27, 1995, which is a continuation-in-part of 515
filed on November 20, 1996, which is a divisional application of 08 / 387,303 named "Aking an Acrylonitrile and Olefinically Unsaturated Polymer"
rocess for Making an Acrylonitrile and Olefinically Unsaturated Polymer "
Is a continuation-in-part application for USSN 08 / 703,718 entitled

[0002]

FIELD OF THE INVENTION

The present invention relates to a thermostable, thermoplastic, melt-fabricable multipolymer of an acrylonitrile monomer, a halogenated monomer and optionally an olefinically unsaturated monomer. The unique assembly of acrylonitrile monomer, halogenated monomer and optionally olefinically unsaturated monomer provides a multipolymer that can be heat processed into nitrile fibers or nitrile products.

The term “multipolymer” refers to polymers, copolymers, terpolymers prepared from at least one of an acrylonitrile monomer and a vinyl halogen monomer, and optionally olefinically unsaturated monomer (s). And multi-polymer are meant.

As specified by the US Federal Trade Commission for modacrylic fiber, “
It is to be understood that the term "modacrylic" comprises 35% to 85% polymerized acrylonitrile units.

[0005]

BACKGROUND OF THE INVENTION

Nitrile polymers are desirable in the manufacture of fibers, films, moldings, packaging and the like. Nitrile polymers have excellent physical, chemical and mechanical properties such as gas and moisture barriers, chemical resistance, rigidity, thermal stability, UV resistance and microbial resistance. However, nitrile polymers, especially nitrile polymers containing halogenated monomers, are degraded during thermal processing due to the presence of a long repeating sequence consisting of both acrylonitrile monomer units and halogenated monomer units in the polymer chain. . Polymers of nitrile and halogen monomers are not melt processable due to the long sequence of nitrile and / or halogen monomer units and require the use of solvents.

Known methods for producing fibers and products made from polymers of nitrile monomers and halogenated monomers are based on solvent technology. Polymers of nitrile monomers and halogenated monomers decompose at their processing temperatures and cannot be processed in the molten state. Polymers of nitrile monomers and halogenated monomers are
Lowers at increasing rates above 150 ° C. The polymer becomes yellow, orange, red and finally black as it becomes lesser. To avoid these problems, the conventional technique of converting polymers of nitrile monomers and halogenated monomers into nitrile fibers or products is by the solution method. Only fibers or products made from solution-based methods are available with current technology. A wider range of thermoformed nitrile products, ie bottles, films, parts, etc., cannot be made from polymers of nitrile and halogenated monomers made by current polymerization processes.

There are many drawbacks to producing nitrile fibers or products by solution-based extrusion processes. In the case of modacrylic fibers, acrylonitrile monomers are copolymerized with halogenated monomers. Incorporation of halogenated monomers reduces the thermal stability of modacrylic polymers. Solution-based methods require the removal of solvent from the resulting fiber or product. Removal of the solvent creates voids in the structure, reducing the dimensional uniformity of the product and compromising the mechanical and barrier properties of the product. In addition, a large amount of solvent needs to be recycled.

It is advantageous to produce fibers or products from thermostable thermoplastic nitrile multipolymers by a solventless melting process. Furthermore, it is desirable that the multipolymer and its products be homogeneous throughout and substantially void free. The thermal stability of the multipolymers herein allows them to be thermoprocessed in the absence of solvent, at higher operating speeds; at the same time with improved physical, mechanical and chemical properties. It is possible to produce a fiber or product having. Furthermore, fibers or products of complex shape and cross section can be produced from melt-processible thermostable thermoplastic multipolymers.

[0009]

[Outline of the Invention]

The present invention is a melt containing about 20% to less than 50% polymerized acrylonitrile, about 80% to about 40% polymerized halogenated monomer, and about 0% to 10% polymerized olefinically unsaturated monomer. A processable multipolymer is provided. The resulting multipolymer is heat stable, thermoplastic and heat processable. The multipolymer contains a relatively uniform distribution of each of the monomers in the multipolymer chain. The present invention provides multi-polymers that are thermostable, thermoplastic and have excellent chemical, mechanical and physical properties.

The present invention provides a method of making a thermostable, thermoplastic multipolymer by polymerizing at least one of an acrylonitrile monomer, at least one halogenated monomer, and optionally at least one olefinically unsaturated monomer. provide.
In the method, the rate of addition of acrylonitrile monomer, halogenated monomer and optionally olefinically unsaturated monomer is equal to or less than the rate of polymerization to maintain the monomer starvation process.

The present invention further provides for melt processing of thermostable thermoplastic multipolymers into fibers or articles in the absence of solvent. Further, the present invention includes fibers that can be used in woven knitted or non-woven applications, including thermoforming, compression molding, extrusion, injection molding, blow molding, including the aforementioned processing steps such as melt spinning. Products are obtained which are heat processed by calendering, thermoforming, fusion coating and the like.

[0012]

[Specific mode]

The unique heat-processable multipolymer used in the present invention comprises an acrylonitrile monomer, a halogenated monomer and optionally an olefinically unsaturated monomer, the multipolymer being homogeneous and having a substantially uniform microscope. Have an organization. Methods for making thermostable thermoplastic multipolymers are described, for example, in “A Process For Making A High Nitrile Multipolymer Prep”.
USPN 5,618,901 named ared From Acrylonitrile and Olefinically Unsaturated Monomers; "A Process For Making An Acrylonitrile Me
USPN5 named thacrylonitrile Olefinically Unsaturated Monomers "
, 602, 222; and "Process For Making Acrylonitrile / Methacrylonitril.
found in USPN 5,596,058 entitled "e Co-polymers".

The multipolymer comprises about 20% to about 5% polymerized acrylonitrile monomer.
Less than 0%, preferably about 30% to less than 50%, more preferably about 40% to 50%
Less than about 80% to about 40% of at least one polymerized halogenated monomer.
, Preferably about 70% to about 40%, more preferably about 65% to 40%, 0% to about 20%, preferably 0% of one or more of the polymerized olefinically unsaturated monomers.
To about 15%, more preferably about 0.1% to about 10%.

The halogenated monomers used in the multipolymer are one or more halogenated monomers that are polymerizable with the acrylonitrile monomer. The halogenated monomers used in the multipolymer can be a single monomer or a combination of monomers. The choice of halogenated monomer or combination of monomers depends on the desired properties (ie flame retardancy) of the resulting multipolymer and product.

As the halogenated monomer, vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene chloride, vinylidene bromide, vinylidene fluoride, halogen-substituted propylene monomer,
Examples include, but are not limited to, aromatic halogen monomers such as chlorostyrene. Preferred halogenated monomers are vinyl chloride, vinyl bromide and vinylidene chloride.

The olefinically unsaturated monomer used in the multipolymer is at least one kind of olefinically unsaturated monomer having a C═C double bond capable of polymerizing with acrylonitrile. Olefinically unsaturated monomers exclude halogenated monomers.
The olefinically unsaturated monomer is optionally used in a multi-monomer mixture, depending on the properties desired for the multi-polymer and the resulting product. The olefinically unsaturated monomer can be a single polymerizable monomer or a combination of polymerizable monomers. The choice of olefinically unsaturated monomer or combination of monomers depends on the desired properties of the resulting multipolymer and product.

Examples of the olefinically unsaturated monomer include acrylate, methacrylate, acrylamide and its derivative, methacrylamide and its derivative, maleic acid and its derivative, vinyl ester, vinyl ether, vinyl amide, vinyl ketone,
Examples include, but are not limited to, styrene, ionic monomers, acid containing monomers, base containing monomers, olefins and the like.

The acrylate includes C ₁ -C ₁₂ alkyl, aryl and cyclic acrylates such as methyl acrylate, ethyl acrylate, and functional derivatives of acrylates such as 2-hydroxyethyl acrylate and 2-chloroethyl acrylate. , But not limited to these. Preferred acrylates are methyl acrylate and ethyl acrylate.

Methacrylates include C ₁ -C ₁₂ alkyl, aryl and cyclic methacrylates such as methyl methacrylate, ethyl methacrylate, phenyl methacrylate, butyl methacrylate, isobornyl methacrylate, 2-ethylhexyl methacrylate, and functional derivatives of methacrylates such as Examples include, but are not limited to, 2-hydroxyethyl methacrylate, 2-chloroethyl methacrylate, and the like. The preferred methacrylate is methyl methacrylate.

Examples of acrylamide and methacrylamide, and N-substituted alkyl derivatives and N-substituted aryl derivatives thereof include acrylamide, methacrylamide, N-methylacrylamide, and N, N-dimethylacrylamide, respectively. Not limited to.

[0021] Maleic acid monomers include, but are not limited to, maleic acid monododecyl maleate, didodecyl maleate, maleimide, N-phenyl maleimide.

Vinyl ethers include, but are not limited to, C _{1 to} C ₈ vinyl ethers such as ethyl vinyl ether, butyl vinyl ether, and the like. Vinyl esters include, but are not limited to, vinyl acetate, propionate, butyrate, and the like. The preferred vinyl ester is vinyl acetate.

Vinylamides include, but are not limited to, vinylpyrrolidone and the like. Examples of vinyl ketones include C ₁ -C ₈ vinyl ketones such as ethyl vinyl ketone,
Examples include, but are not limited to, butyl vinyl ketone.

Examples of styrene include, but are not limited to, substituted styrene, polysubstituted styrene, methylstyrene, styrene, and indene. Styrene has the following formula:

[0025]

[Chemical 1]

(Wherein each of A, B, D and E is independently selected from hydrogen (H), a C ₁ -C ₄ alkyl group, and halogen). Ionic monomers include, but are not limited to, sodium vinyl sulfonate, sodium styrene sulfonate, sodium methallyl sulfonate, sodium acrylate, sodium methacrylate, and the like. Preferred ionic monomers are sodium vinyl sulfonate, sodium styrene sulfonate and sodium methallyl sulfonate.

Acid-containing monomers include, but are not limited to, acrylic acid, methacrylic acid, vinyl sulfonic acid, itaconic acid, styrene sulfonic acid, and the like. Preferred acid containing monomers are itaconic acid, styrene sulfonic acid and vinyl sulfonic acid.

Examples of the base-containing monomer include vinyl pyridine, 2-aminoethyl-N-acrylamide, 3-aminopropyl-N-acrylamide, 2-aminoethyl acrylate and 2-aminoethyl methacrylate, but are not limited thereto. Not done.

As the olefin, isoprene, butadiene, C _{2 to} C ₈ straight chain and branched chain α
-Olefins such as propylene, ethylene, isobutylene, diisobutylene,
1-butene and the like can be mentioned, but the invention is not limited thereto. Preferred olefins are isobutylene, ethylene and propylene.

The choice of olefinically unsaturated monomer or combination of monomers depends on the desired properties of the resulting multipolymer and its end use. Polymerizing acrylonitrile monomers with halogenated monomers increases the flame resistance of the multipolymer and the flame retardancy of its final product. For example, polymerizing acrylonitrile monomers, halogenated monomers and α-methylstyrene and / or indene gives multipolymers with flame resistance, improved heat distortion temperature and glass transition temperature and their final products. Polymerizing acrylonitrile monomer, halogenated monomer, and isobutylene improves the flexibility of the multipolymer and its final product. Polymerization of acrylonitrile monomers, halogenated monomers, and acrylates and / or methacrylates improves the processability of the multipolymer and its final product. Polymerizing an acid-containing monomer, a base-containing monomer and / or a hydroxyl group-containing monomer with an acrylonitrile monomer and a halogenated monomer improves dyeing suitability of the resulting multipolymer and is a useful dye site.
) Is provided.

In the practice of the present invention, the polymerization process is carried out as an emulsion, solution, suspension or in continuously added bulk. The present invention can be carried out as a semi-batch method or a continuous method.
Preferably, the polymerization process is carried out as an emulsion or suspension. The process of the present invention is not carried out in a batch process as defined herein as the first charge of all reactants in the reactor prior to initiation of polymerization.

First, the acrylonitrile monomer, the halogenated monomer and optionally the olefinically unsaturated monomer are added in an amount of about 0.1 based on the total weight of the polymerization reaction medium.
% To about 15% by weight in an aqueous medium. The initial multi-monomer mixture comprises about 5 wt% to less than about 50 wt% acrylonitrile monomer, about 10 wt% to about 90 wt% halogenated monomer, and about 0 wt% to about 20 wt% olefinically unsaturated monomer. Including.

The aqueous medium contains water and a suitable surfactant such as an emulsifier or dispersant. Surfactants and their use are known to those skilled in the art. The molecular weight modifier is about 0 wt% to about 5 wt%, preferably about 0.1 wt% to 4 wt% based on the total weight of the multimonomer mixture, based on the initial multimonomer mixture.
%, And most preferably about 0.1% to about 3% can be added.

The initial multi-monomer mixture is placed in a reactor containing an aqueous medium. The reactor with the aqueous medium is purged with an inert gas such as nitrogen, argon and the like. Preferably, but optionally, purging with an inert gas continues during the polymerization reaction. Next, the initial multi-monomer mixture is heated to about 20 ° C. to about 120 ° C.
Heat to about 80 ° C. The temperature of the polymerization reaction is about 20 ° C. to about 120 throughout the process.
C., preferably about 10.degree. C. to about 80.degree.

An initiator is added to the initial multi-monomer mixture to initiate the polymerization reaction. The initiator is generally about 0.01% by weight, based on the total weight of the multi-monomer mixture.
Add about 5% by weight.

Once the polymerization reaction has begun, a multi-monomer feed mixture consisting of acrylonitrile monomer, halogenated monomer and optionally olefinically unsaturated monomer is added continuously to the polymerization reaction in the reactor. The total weight of unreacted acrylonitrile monomer, unreacted halogenated monomer and unreacted olefinically unsaturated monomer present in the polymerization mixture is always about 20 based on the weight of the polymerization mixture.
% Or less, preferably about 15% or less, most preferably about 10% or less.

The multi-monomer feed mixture comprises about 5% by weight to about 5% acrylonitrile monomer.
Less than 0% by weight, from about 10% to about 90% by weight halogenated monomer, and from 0% to about 20% by weight olefinically unsaturated monomer. The molar ratio of acrylonitrile monomer, halogenated monomer and olefin unsaturated monomer in the multi-monomer feed mixture is fixed and kept constant throughout the polymerization process to obtain a homogeneous multi-polymer. The feed molar ratio of acrylonitrile monomer to halogenated monomer to olefinically unsaturated monomer varies depending on the desired multipolymer composition.

A molecular weight modifier is optionally added to the polymerization mixture. Preferably, the molecular weight regulator is added continuously to the polymerization mixture. The molecular weight modifier is preferably from about 0 wt% to about 5 wt%, preferably from about 0.1 wt% to about 4 wt%, most preferably based on the total weight of the multi-monomer mixture, based on the polymerization reaction medium. Is added at about 0.1% to about 3% by weight.

Molecular weight regulators include, but are not limited to, mercaptans, alcohols, halogen compounds, or any other chain transfer agent known to one of ordinary skill in the art. Mercaptan is a preferred molecular weight regulator and includes mono-mercaptans, polyfunctional mercaptans or combinations thereof. The mercaptan is a straight chain, branched chain, substituted or unsubstituted C ₅ -C ₁₈ alkyl mercaptan, and includes, for example, d-limonene dimercaptan, but is not limited thereto. Preferred mercaptans are straight chain, branched chain, a C ₅ -C ₁₂ alkyl mercaptans substituted or unsubstituted, for example, t- dodecyl mercaptan and n- octyl mercaptan.
The molecular weight modifiers can be used alone or in combination. The molecular weight regulator can be the same or different molecular weight regulator used for the initial multi-monomer mixture.

Molecular weight regulators, which may be useful, regulate the molecular weight of the multipolymer polymerized by terminating the growing chains. The molecular weight modifiers useful in the present invention produce multipolymers having a molecular weight of about 15,000 to about 500,000.

The initiator is typically added to the polymerization mixture continuously or slowly as a single solution. The initiator is added at a rate that maintains the rate of polymerization. One of ordinary skill in the art can determine the rate. The initiator concentration is generally from about 0.01% to about 5% by weight, based on the total weight of the multi-monomer mixture.

The initiator is any free radical initiator known to those skilled in the art. Initiators include, but are not limited to, azo compounds, peroxides, hydroperoxides, alkyl peroxides, peroxydicarbonates, peroxyesters, dialkyl peroxides, persulfates, perphosphates and the like. The preferred initiator is persulfate. The initiators can be used alone or in combination with reducing compounds to improve reactivity (redox). The initiator is
It can be the same or different initiator that was used to initiate the polymerization reaction.

The polymerization mixture is agitated by known methods, for example by stirring and shaking. The reaction was allowed to continue until the polymerization proceeded to the desired degree, generally about 30% to about 90% conversion.

The polymerization reaction is by cooling; by adding interfering agents such as diethylhydroxylamine and 4-methoxyphenol; by stopping the feed of the multi-monomer feed mixture; removing unreacted monomers, etc. Stop by. Initiators and their use are known to those skilled in the art.

At the end of the polymerization reaction, the multipolymer is a solid, slurry or latex. Any known method may be used, for example crumb coagulation, spraying a solution of the multipolymer into a heating chamber and / or a vacuum chamber to remove water vapor, stripping, filtering and centrifuging. The multipolymer may thus be isolated.

The multipolymer produced by the process of the present invention comprises a thermostable thermoplastic multipolymer comprising polymerized acrylonitrile monomer, polymerized halogenated monomer and optionally polymerized olefin unsaturated monomer. It is a polymer. The multipolymer is homogeneous in that the composition and order of the multipolymer produced is substantially the same throughout the process.

The method of producing the thermostable thermoplastic meltable multipolymer from the monomers is accomplished by adjusting the addition rate of the acrylonitrile monomer, the halogenated monomer and the olefin unsaturated monomer to the polymerization rate. The process of the present invention is a monomer starvation process in which the polymerization reaction rate exceeds or equals the addition rate of the multi-monomer feed mixture. The low concentration of unreacted multimonomer during the polymerization process results in a monomer starvation condition that prevents a long sequence of individual monomers in the multipolymer chain. Multi-polymer chains are, for example, AN-AN-Z-AN.
-AN-ZZ-AN-ZZ (AN = acrylonitrile units and Z = halogen units), of the polymerized halogenated monomer interdispersed between the short sequence of polymerized acrylonitrile monomers. Including a short hierarchy. The halogenated monomers are substantially uniformly interdispersed among the acrylonitrile units in the multipolymer. These shorter acrylonitrile-sequenced multipolymers have lower melting points and also have reduced melt viscosities that allow melting / thermoprocessing in the absence of solvent. The multipolymer has unique properties in the fiber or product,
For example, it can exhibit dimensional stability, improved orientation, substantially void-free, homogeneity, strength, toughness, flexibility, resistance to UV light degradation, and microbial resistance.

Thermostable thermoplastic multipolymers can be prepared by any of the thermal processing and / or thermoforming techniques.
It can be processed by combining two or more. The multipolymer is thermoplastic, thermostable and thermoprocessable without the addition of solvents. The multipolymer of the present invention can be further heat processed without solvent by spinning, molding, extrusion and the like. Such thermal processing steps include thermoforming, orientation, blowing, laminating, coating, extrusion, sealing, pre-stretch compression molding, injection molding,
Examples include, but are not limited to, blow molding, calendering, and melt coating. The thermal processing temperature is higher than the glass transition temperature of the multipolymer and is about 100 ° C to about 300 ° C, preferably about 130 ° C to about 240 ° C.

Exemplary Method of Making Melt-Spun Acrylonitrile Olefinically Unsaturated Fibers,
And the process of making the fiber is "Melt Spun Acrylonitrile Olefinically Unsa
USSN named "turated Fibers and the Process to Make the Fibers"
08 / 574,312 and 08 / 780,754. An exemplary method for making hot melt processable products from multipolymers is "Thermally Melt Processa
ble Multipolymers of Acrylonitrile and Olefinically Unsaturated Monomers
Is described in USSN 09 / 255,092.

The multipolymers and the resulting products contain lubricants, dyes and leaching agents.
agent), pigments, matting agents, stabilizers, static control agents,
It will be readily appreciated by those skilled in the art that further improvements can be made by adding antioxidants and toughening agents such as fillers. It is understood that any additive capable of doing so can be used as long as it has no deleterious effect on the thermal properties of the multipolymer and its product.

Thermal processing is carried out in the absence of solvent. Products manufactured here include uniaxial and / or biaxial films, sheets, tapes, laminates, shaped articles, coated structures, composite structures, and fibers. Multipolymers are used in many applications, for example filaments, fibers, woven fabrics, woven fabrics, non-woven fabrics, flame-retardant fabrics, films, carbon sheets, carbon films, sheets, pipes, pipes, moldings, coating laminates, wire coatings, xerography. Can be used in substrates, packaging, tapes, bottles, coatings, laminates, barrier products, membranes, molded articles and the like. The products of the invention can further be used in packaging, barrier applications, electrical insulation, photographic films, engineering films and the like.

[0052]

【Example】

The following examples are provided to illustrate the invention, but it should be understood that the invention is not limited to the particular details described in the examples below.

Example 1 Preparation of 50/50, Acrylonitrile / Vinyl Chloride Copolymer: A 1 liter stainless steel polymerization reactor capable of holding pressure at about 150 psi. With a stirrer, electric heater and conditioning system, nitrogen purge, and One pumped monomer mixture feed line was attached. First, the reactor was charged with about 560 g of water and about 22.9 g of Dowfax 8390 (a surfactant commercially available from Dow Chemical Co.), purged with nitrogen gas, sealed and then charged to about 22 g. ℃.
An initiator system consisting of about 1.28 g of ammonium persulfate, about 0.3 g of sodium metabisulfate and about 0.08 g of ferrous sulfate was immediately added thereto, under pressure, about 0.94 g of acrylonitrile, about vinyl chloride. An initial monomer mixture consisting of 15.1 g and about 0.32 g of n-octyl mercaptan was charged. A monomer feed consisting of about 45.2 g of acrylonitrile, about 105.4 g of vinyl chloride and about 3.0 g of n-octyl mercaptan was then added to the reactor in a uniform manner over 3 hours. The reaction was allowed to proceed for 30 minutes after the feed was completed, then excess vinyl chloride gas was vented from the reactor and the latex produced was vented from the reactor. The reaction temperature is about 2
The temperature was from 2 ° C to about 28 ° C. The latex is about 95 containing about 4 g of magnesium sulfate.
Coagulated in 3 liters of stirred water at 0 ° C., filtered and dried.

[0054]   The final conversion to copolymer based on all monomers is 60%, ¹³ According to C NMR, its composition had about 48.7% by weight of acrylonitrile.
And molecular weight M_wIs 22,000 according to gel permeation chromatography (GPC)
0, and the melt index is 47 (g / 10 at 200 ° C with a load of 10 kg.
Minutes).

Example 2 40/60, Acrylonitrile / Vinyl Chloride Copolymer: A 1 liter stainless steel polymerization reactor capable of maintaining pressure at about 150 psi. With stirrer, electric heater and conditioning system, nitrogen purge, and pump. One monomer mixture feed line was attached. First, the reactor was charged with about 560 g of water and about 22.9 g of Dowfax 8390 (a surfactant commercially available from Dow Chemical Co.), purged with nitrogen gas, sealed and then charged to about 22 g. ℃.
An initiator system consisting of about 1.28 g of ammonium persulfate, about 0.3 g of sodium metabisulfate and about 0.08 g of ferrous sulfate was immediately added thereto, under pressure, about 0.94 g of acrylonitrile, about vinyl chloride. An initial monomer mixture consisting of 15.11 g and about 0.32 g of n-octyl mercaptan was added. A monomer feed consisting of about 28.6 g of acrylonitrile, about 122.0 g of vinyl chloride and about 3.0 g of n-octyl mercaptan was then added to the reactor in a uniform manner over 3 hours. The reaction was allowed to proceed for 30 minutes after the feed was completed, then excess vinyl chloride gas was vented from the reactor and the latex produced was vented from the reactor. The temperature of the reaction was about 22 ° C to about 28 ° C. Latex is about 9 containing about 4 g of magnesium sulfate.
Coagulated in 3 liters of stirred water at 5 ° C., filtered and dried.

The final copolymer has a composition of about 41.2 wt% acrylonitrile by ¹³ C NMR, a molecular weight M _w of 50,000 by gel permeation chromatography (GPC) and a melt index of 10 kg. 8 at 200 ° C under load
It was 5 (g / 20 minutes).

Example 3 Copolymer of acrylonitrile and vinylidene chloride (47/53, AN / V
Preparation of DC) In a 2 liter glass polymerization kettle equipped with a temperature controlled water jacket, a flat blade stirrer, an inert gas barge line, and three feed lines with a pump, 757 g of distilled water, Dowfax 8390 ( About 18.86 g of a surfactant commercially available from Dow Chemical Co.), about 11 g of acrylonitrile, about 11 g of vinylidene chloride, and about 0.18 g of n-octyl mercaptan were added, and the mixture was heated to about 9 ° C. in the presence of nitrogen gas. . About 0.22 g of sodium metabisulfate, about 0.44 g of ferrous sulfate and about 0.22 g of ammonium persulfate were added thereto to start the reaction. At the start, three continuous streams were uniformly pumped into the reactor for 5 hours. Flow 1
Consisted of about 89.1 g of acrylonitrile, about 108.9 g of vinylidene chloride and about 1.58 g of n-octyl mercaptan. Stream 2 consisted of about 0.55 g ammonium sulfate in 100 g water. Stream 3 consisted of about 0.04 g ferrous sulfate in 100 g water.

After 5 hours, the latex produced was coagulated in 3 liters of warm water containing about 6 g of Al ₂ (SO ₄ ) ₃ . Collect the polymer by filtration and in a fluid bed at about 60 ° C.
And dried for 5 hours. The conversion is 84.5% and the composition is about 47.3% by weight AN.
And VDC 53.7% by weight, and the molecular weight M _w was 202,000 by gel permeation chromatography (GPC).

Example 4 Preparation of Acrylonitrile, Vinylidene Chloride and Methyl Acrylate Terpolymer 2 liters equipped with temperature controlled water jacket, flat blade stirrer, inert gas barge line, and one feed line with pump. 600 g of distilled water, about 28.57 g of Dowfax 8390 (a surfactant commercially available from Dow Chemical Co.), about 7.6 g of acrylonitrile, about 11 g of vinylidene chloride (VDC), and methyl acrylate (MA). ) About 1.4 g and n-octyl mercaptan about 0.20 g were added, and the mixture was heated to about 18 ° C in the presence of nitrogen gas. About 0.40 g of sodium metabisulfate, about 0.10 g of ferrous sulfate and about 1.2 g of ammonium persulfate were added thereto to start the reaction. At the beginning, a continuous stream of about 68.4 g of acrylonitrile, about 99.0 g of vinylidene chloride, about 12.6 g of methyl acrylate and about 1.8 g of n-octyl mercaptan was pumped into the reactor uniformly for about 3 hours. . After the addition was complete, the reaction was continued for 30 minutes.

After 3 hours and 30 minutes, the produced latex was coagulated in 3 liters of warm water containing about 6 g of MgSO ₄ . The polymer is collected by filtration and about 60 in a fluidized bed.
It was dried at ℃ for about 5 hours. The conversion rate is 82.45% and the composition is AN about 43.3.
% By weight, VDC 48.2% by weight and MA 8.5% by weight.

From the above description of examples and inventions; those skilled in the art will perceive improvements, changes and modifications in the invention. Such improvements, changes and modifications are intended to be covered by the appended claims.

─────────────────────────────────────────────────── ─── Continued front page    (81) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, I T, LU, MC, NL, PT, SE), OA (BF, BJ , CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, K E, LS, MW, MZ, SD, SL, SZ, TZ, UG , ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AG, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, BZ, C A, CH, CN, CR, CU, CZ, DE, DK, DM , DZ, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, K E, KG, KP, KR, KZ, LC, LK, LR, LS , LT, LU, LV, MA, MD, MG, MK, MN, MW, MX, MZ, NO, NZ, PL, PT, RO, R U, SD, SE, SG, SI, SK, SL, TJ, TM , TR, TT, TZ, UA, UG, UZ, VN, YU, ZA, ZW (72) Inventor Parsec, Elena Simona             Pennsylvania, United States 19103,             Philadelphia, South Twenty             Fifth Street 201, Locust             On the park (72) Inventor Wu, Muyen             Hadso, 44236, Ohio, United States             Rondo Nilly Boulevard             5778 F-term (reference) 4F071 AA20 AA22 AA23 AA24 AA25                       AA26 AA28 AA30 AA33 AA34                       AA35 AH01 AH03                 4J100 AB02R AB08Q AC03Q AC04Q                       AC11Q AC12Q AG04R AJ09R                       AL03R AM02P AM15R BB03Q                       JA11 JA43 JA64

Claims (14)

[Claims] 1. About 20% to less than 50% by weight of polymerized acrylonitrile, about 80% to about 40% by weight of polymerized halogenated monomer, and about 0% of polymerized olefinically unsaturated monomer. % To 15% by weight, and a thermostable, thermoplastic, multi-polymer composition that is heat processable in the absence of solvent. 2. About 30% to less than 50% by weight of polymerized acrylonitrile, about 70% to about 40% by weight of polymerized halogenated monomer, and about 0% of polymerized olefinically unsaturated monomer. %. 10% by weight of a composition, and a thermostable thermoplastic, composition which is thermoprocessable in the absence of solvent to form a multipolymer. 3. A polymerized acrylonitrile of about 40% to less than 50% by weight, a polymerized halogenated monomer of about 65% to about 40% by weight, and a polymerized olefinically unsaturated monomer of about 0. The composition of claim 1 which comprises 1 wt% to 10 wt% and is a thermostable, thermoplastic, multi-polymer heat-processible in the absence of solvent. 4. The halogenated monomer is selected from vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene chloride, vinylidene bromide, vinylidene fluoride, halogen-substituted propylene monomer, aromatic halogen monomer, chlorostyrene, and combinations thereof. The composition of claim 1 selected from the group consisting of: 5. The composition of claim 1 wherein said halogenated monomer is selected from the group consisting of vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene chloride. 6. The olefinically unsaturated monomer contains an acrylate, a methacrylate, an acrylamide and a derivative thereof, a methacrylamide and a derivative thereof, a maleic acid and a derivative thereof, a vinyl ester, a vinyl ether, a vinylamide, a vinyl ketone, a styrene, an ionic monomer and an acid. Monomer, base-containing monomer,
The composition of claim 1 selected from the group consisting of olefins, and combinations thereof. 7. The olefinically unsaturated monomer is methyl acrylate,
Claims selected from the group consisting of ethyl acrylate, methyl methacrylate, sodium vinyl sulfonate, sodium styrene sulfonate, sodium methallyl sulfonate, itaconic acid, styrene sulfate, vinyl sulfonic acid, isobutylene, ethylene, propylene, and combinations thereof. Item 1. The composition according to Item 1. 8. A method for producing a nitrile multipolymer by polymerizing an acrylonitrile monomer, one or more halogenated monomers, and an olefin unsaturated monomer, wherein the method comprises about 5% by weight to about acrylonitrile monomer. Less than 50% by weight, from about 10% to about 9% of at least one halogenated monomer.
Heating an initial multimonomer mixture comprising 0% by weight and 0% to about 20% by weight of at least one olefinically unsaturated monomer at a temperature of about 20 ° C. to about 120 ° C .; an initiator for the initial multipolymer mixture. To start the polymerization reaction; about 5% to less than about 50% by weight of acrylonitrile monomer, at least 1
A halogenated monomer of about 10% to about 90% by weight and at least one olefinically unsaturated monomer of about 0% to about 20% by weight, the multipolymer feed mixture comprising: The feed mixture is characterized as being fixed and constant throughout the polymerization process, and the rate of addition of the multipolymer feed mixture is slow or equal to the rate of polymerization to produce a thermostable thermoplastic multipolymer. Production method. 9. The halogenated monomer is vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene chloride, vinylidene bromide, vinylidene fluoride, halogen-substituted propylene monomer, aromatic halogen monomer, chlorostyrene, and combinations thereof. 9. The method of claim 8 selected from the group consisting of: 10. The olefinically unsaturated monomer is methyl acrylate, ethyl acrylate, methyl methacrylate, sodium vinyl sulfonate, sodium styrene sulfonate, sodium methallyl sulfonate, itaconic acid, styrene sulfuric acid, vinyl sulfonic acid, isobutylene, ethylene. 9. The method of claim 8 selected from the group consisting of :, propylene, and combinations thereof. 11. The following steps: (a) about 20% to less than about 50% by weight of acrylonitrile monomer, vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene chloride, vinylidene bromide, vinylidene fluoride. From about 80% to about 40% by weight of at least one halogenated monomer selected from the group consisting of halogen-substituted propylene monomers, aromatic halogen monomers, chlorostyrenes, and combinations thereof, methyl acrylate, ethyl acrylate, Olefin unsaturation selected from the group consisting of methyl methacrylate, sodium vinyl sulfonate, sodium styrene sulfonate, sodium methallyl sulfonate, itaconic acid, styrene sulfate, vinyl sulfonic acid, isobutylene, ethylene, propylene, and combinations thereof. Monoma Preparing a thermostable thermoplastic nitrile monomer comprising polymerizing at least one of from about 20% to about 10% by weight; and (b) about 260 above the glass transition temperature of the multipolymer. A step of thermally processing the multipolymer in the absence of a solvent at a temperature of up to ℃, melt spinning, compression molding, continuous extrusion, injection molding, extrusion molding, blow molding, calendering, thermoforming, orientation. A hot melt processing step selected from the group consisting of: laminating, melt coating, and combinations thereof. 12. The method according to claim 11, wherein the hot melt processing temperature is 130 ° C. to 240 ° C. 13. The method of claim 11, wherein the molded article is selected from the group consisting of filaments, tows, tops, staples, continuous filaments, yarns, nonwovens, wovens, and combinations thereof. 14. The molded product is a film, sheet, tape, laminate, coated structure, composite structure, pipe, carbon sheet, carbon film, molded product, coated laminate, wire coating, membrane, and combinations thereof. The method of claim 11 selected from the group consisting of: