JPS6038404B2 - Imidized acrylic acid polymer composition and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing imide polymers, in which a polymer containing imide units and an acrylic acid polymer are imidized to a desired degree without adding water or solvent. It is about the method.

For the basic reaction of forming imides by reacting ammonia, butylamine, dodecylamine or octylamine with polymethyl methacrylate, Gr.
U.S. Patent No. 214,620y, German Patent No. 1077872 and German Patent No. 12 to Aves.
It is listed in number 4236.

U.S. Patent No. 32844 to Schr6der et al.
25 and British Patent No. 92662y, a method is described for imidizing acrylics by reacting polymethyl methacrylate with ammonium hydroxide, ammonium phosphate, alkyl amines, or after partial reaction with ammonium hydroxide to imidize alkyl methacrylates. A method is described for imidizing acrylics in combination with a method of reaction with an amine. In British Patent No. 104522y, 18
A method is described for chemically transforming methacrylic acid/methacrylonitrile (h-side A/MAN) polymers or turbo remers by heating at 0.00 to 3000°C. German Patent No. 1247517, No. 2041
No. 736 and No. 2,047,096 describe a method for forming an imide by heating a methacrylamide/methyl methacrylate (MAN/MMA) copolymer and an inert solvent to generate ammonia. Most of the prior patents and publications relating to the imidization of acrylics by reacting ammonia and primary amines with polymethyl methacrylate, such as U.S. Pat.
No. 4425 relates to an autoclave batch process that requires extended heating times, typically 7 hours or more, in the presence of an inert dissolving or suspending solvent. In U.S. Pat. No. 3,557,07, an ethylene-isopropyl methacrylate copolymer is heated to the decomposition temperature of isopropylester (325o0) to form anhydrous methacrylic units, and then Ethylene/methacrylic acid/methacrylamide turbolimer is produced from the above ethylene isopropyl taacrylate by reacting the unit with gaseous ammonia to obtain methacrylamide and methacrylic acid residues in the polymer chain. The method is described. The above reactions are carried out in pure form without the use of solvents, and in the examples are shown in the decomposition "region".
is listed. Although there is no description in the above patent that the above reaction is carried out in an extruder, the order of the above patent is
The abstract states that these reactions can be carried out in an extruder. An example of using an extruder as a polymer reactor has already been described in connection with the process for producing copolyesters (method for polymerizing copolyesters in an extruder with a discharge port and its properties - J.A.
ppliedPolymerScieMe12, 240
3 (1968), Nylon products (method for straight-twill extrusion of nylon products from lactams - M em Plastics
, August 1969 - War Pfleider
er) and a method for graft polymerization of polyolefins (S
Teinkamp et al., US Pat. No. 62,265).

German Patent No. 1,077,872 describes a method for imidizing acrylic acid polymers using an extruder using an aqueous solution of ammonia. However, the product produced by this method is a foamed fiber with poor thermal stability that requires further processing before it can be used to make useful products. Additionally, the above process is commercially impractical in that the foamed polymer emits free ammonia vapors as it is extruded from the extruder under high pressure. It is an object of the present invention to provide a method for imidizing acrylic acid polymers with short residence times.

Another object of the present invention is to ensure that the polymers produced have a high uniform molecular weight, are free of cross-linking, are thermoplastic, and have improved thermal stability, without substantially reducing the molecular weight. An object of the present invention is to provide a method for imidizing acrylic acid polymers. It is also a further object of the present invention to provide a method for producing acrylic acid polymers which are capable of imidizing to less than substantially complete imidization, in particular uniformly imidized polymers. It is to provide. Still another object of the present invention is to provide new imidized acrylic acid polymers. Yet another object of the present invention is to provide an improved process for producing imide polymers having improved properties without the disadvantages of conventional production methods. The above objectives and other matters will become apparent from the following disclosure of the invention.

The above objects are achieved by the present invention, and one aspect of the present invention is to react an acrylic acid polymer with anhydrous ammonia or anhydrous primary amine in an extruder without using water or a solvent. The present invention relates to a method for producing a polymer containing imide units, which is characterized by applying pressure below atmospheric pressure to two discharge ports. Another aspect of the invention relates to polymeric products containing imide units made by the above method.

The thermoplastic polymer that is part of this invention contains imide units having the chemical formula: In the formula, R,, R2 and R3 are each hydrogen, an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an allyl group, an aralkyl group, an alkaryl group or a mixture of the above groups.

Another feature of the above polymer is that it has no cross-linking, is soluble in dimethylformamide, and is soluble in TGA.
The polymer has high thermal stability, decomposing 1% in air at temperatures of about 285 qo or higher, as measured by the above method. Dynamic thermogravimeter analysis (dy-like MLC ratio ermogay; me
mcanal, (TGA)), duPont
lnstmment Products
DivisionPrelimiMryProduc
The temperature was increased by 20 oo per minute according to the program in air or nitrogen using a Dupont thermogravimeter analyzer coupled to a differential temperature analyzer as described in Bulletin 950-1 (A-36177). It is a standard test.

Acrylic acid polymers are all polymers containing units derived from esters of acrylic or methacrylic acid.

The acrylic acid polymer can be either monolayer or multilayer, but in the case of multilayer, the outer or final layer must contain units derived from acrylic acid or methacrylic acid. This is because it is believed that the imidization reaction takes place primarily in this outer or final layer. On the other hand, all of the acrylic esters or methacrylic esters mentioned above may contain acrylic acid polymers, and may contain any amount of polymer. Generally speaking, at least 25% by weight
, preferably at least about 5% by weight, more preferably about 8% by weight, and most preferably about 95-10% by weight of the acrylic acid polymer. Among these types of esters, the preferred ones are those in which half of the esters contain 1 to 20 carbon atoms, and the preferred one is methyl methacrylate (M
MA). Monomeric polymers containing at least 8% MMA are highly suitable. Acrylic acid polymers can contain units derived from other ethylenically unsaturated monomers, such as monomers such as styrene, acrylonitrile, and butadiene. The acrylic acid polymer can be a single layer polymer or a multilayer polymer such as a core-seal polymer or a graft polymer with varying degrees of grafting between each layer. The molecular weight of acrylic acid polymers can vary over a wide range.

This is because the intrinsic viscosity of commercially available acrylic acid polymers is
This is because F ranges from about 0.01 or less to about 7.0 or more. Intrinsic viscosity is 7
．． Needless to say, zero or more is preferable. Acrylic acid polymers having an oMF of about 0.28 to 2.0 are most preferred. The starting material now consists of a single layer polymer mixed in the dry or molten state with a multilayer impact modifier polymer.

In this case, monolayer polymers and primarily the outer layers of multilayer polymers are imidized. The above mixtures are more compatible than mixtures of imidized single layer polymers and the same multilayer polymers. Particularly if the latter is not imidized, the above mixtures have higher compatibility. A mixture of a single layer acrylic acid polymer and about 10-6% by weight of a multilayer polymer is preferred. The acrylic acid polymer may be in any shape.

However, moldable powders or granules are generally used. The acrylic acid polymer may be colorless or colored. However, in some cases, dyes or pigments may be adversely affected by imidization. In such cases, the colorant is added after imidization is complete. Ammonia or primary amine is R3
It is a compound with a chemical formula called Nratio.

In the formula, R3 is hydrogen or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an allyl group, an aralkyl group or an alkaryl group. Substantially anhydrous ammonia or primary amine or mixtures thereof are introduced into the reaction zone in gas or liquid form under pressure.

However, in the case of primary amines, they can be introduced in solid form. Among the compounds having the chemical formula R3N ratio, the most preferred are ammonia and methylamine because they are very easily available. However, other materials work very well in this process and produce highly desirable products as well. Other suitable amines are, for example, as follows. Ethyl, n-propyl, n-butyl, heptyl, hexyl,
Octyl, nonyl, decyl, dodecyl, hexadecyl,
Octadecyl, isoptyl, sec-butyl, tertiary-butyl,
Isopropyl, 2-ethyl hexyl, phenethyl, allyl, alanine, benzyl, parachlorobenzyl and dimethoxy phenethyl amines; alanine; glycine; 3'-aminoacetophenone: 2-aminoanthraquinone, and p-family /benzoic acid. The following substances are also recognized as suitable substances. Namely, cyclohexyl amine, 3-aminophthalimide, aniline, flomoaniline, dibromoaniline, triproaniline, chloroaniline, dichloroaniline, trichloroaniline, p-phenetidine, p-toluidine. The important thing is
The amount of water introduced with ammonia or primary amines should be very small or zero. Never introduce more than about 2% water by weight based on ammonia or primary amine. It is desirable that the number of water children introduced is 1% or less. The term substantially anhydrous, as used for the purposes of this invention, is defined as containing the maximum amount of water described above. According to the process of the present invention, the acrylic acid polymer is continuously fed to the extruder and ammonia or primary amine is also continuously introduced at the same time, usually through an inlet.

Unwanted by-products and excess ammonia or primary amines are removed by gradually reducing the pressure at the downstream outlet of the extruder. In this case, at least one downstream outlet is placed in a vacuum (pressure below atmospheric pressure). In some cases, maintaining a vacuum on one outlet is sufficient to adequately remove all by-products and unreacted ammonia or primary amines. The temperature within the extruder may vary depending on the nature of the starting materials, pressure, residence time, etc.

However, a particularly important factor determining extruder temperature is the melt viscosity of the polymer being extruded. Usually about 300o
~37500 is appropriate. But generally speaking,
The minimum and maximum external temperature of the extruder is about 200° to 450°C. Different sections of the extruder-reactor can be maintained at different temperatures. It is preferable to use as high a pressure as possible.

However, as with temperature, the optimum pressure will depend on other factors such as the critical pressure of the equipment, etc. It can be operated at pressures as low as atmospheric pressure, or as high as 100 ppm. In most embodiments, pressures of less than 50 hydrophobic pressures are suitable. If the primary amine is introduced in solid form,
Rather than introducing through a separate additional gateway, it can be introduced in the form of a dry mixture with the acrylic acid polymer. Reaction time (i.e. average residence time in the reaction zone)
is about 0.1 to 100 sand, preferably about 30 to 3
0 sand. In the process of the present invention, the degree of imidization of the acrylic acid polymer can be easily controlled,
Different degrees of imidization can be selected depending on the various properties required of the final product.

The required degree of imidization described above can be consistently achieved by adjusting reaction barometers such as residence time. It is possible to perform imidization with a concentration of 1%, but in order to clearly improve the properties of acrylic acid polymers to the extent that they can be recognized, a minimum of 10% is required.
imidization is usually necessary. According to the method of the invention,
Imidization of about 100% of the yield can be easily achieved. This means that virtually all of the ester halves of the acrylic acid polymer are converted into glutarimide half molecules. The process of the invention does not require a catalyst.

This results in the fins having the great advantage of not having to remove the catalyst. However, it is likely that production rates can be increased by using smaller amounts of catalyst. Solvents are not required and are preferably not used.

The product is extruded from the extruder in molten form, at which point other additives such as fibers, pigments, and elutriants can be incorporated. If deemed necessary,
Additives such as impact modifiers, pigments, fibers, stabilizers, lubricating oils can be added to the acrylic acid polymer before it is introduced into the reactor. The product can then be solidified into any desired shape, such as sheets, tubes, films, strings or lacquered threads.
The solidified product can also be made into powder or granules if necessary. Impact modifiers based on A (acrylonitrile/ptadienostyrene), M (methyl methacrylate/butadiene/styrene) and all acrylic types, while retaining the high working temperatures of imide polymers. , is known to help improve its impact strength. The proportion of impact modifier to imide polymer varies over a wide range depending on the degree of impact improvement required for a particular application. A practical range of impact modifier to imide polymer ratio is from about 1:99 to about 7:30, with a preferred range of about 5:99 to about 7:99.
From 95 to 65 to 40. The impact modifier may be a single layer polymer or a multilayer polymer. If a multilayer polymer is used, the impact modifier may be hard or soft in the first or "center"layer;
Subsequent layers may have varying hardness or softness. Examples of impact modifiers include 1970 King June 1
U.S. Patent Application S.M.O.S. N. Fifth
No. 88,544 and US Pat. No. 3,808,180, issued April 30, 1978. From about 0.1 to about 25 weight percent of the key fuel material can be used.

Preferred elutriation materials include bromine, chlorine, antimony,
There are compounds of phosphorus, aluminum trihydrate, certain organic compounds with two or more hydroxyl groups, or mixtures thereof. More specific examples include triphenyl phosphate, phosphonium bromide, phosphonium oxide, tris(dipromopropyl) phosphate, cycloaliphatic chloride, chlorinated polyethylene, antimony oxide, ammonium polyphosphate, decabromodiphenyl phosphate, There are ethers and chlorinated polyphosphates. Because of the high operating temperature of the polyglutaramide contained in the base resin, a greater amount of gluing material can be added than the gluing material soil that can be added to other base resins.
Moreover, high working temperatures are still maintained. A wide variety of fillers can be used. The filler grass that can be added is about 5-80%. Maximum about 6
Surprisingly large amounts of filler, such as hydrated alumina, ranging from 0 to 70%, can be mixed with the glutarimide polymer base resin. Moreover, in this case the thermoformability remains as before. On the other hand, if you want to maintain your heat and morning glow,
Most thermoplastics cannot contain more than about 40% active filler. The novel imide polymers according to the present invention are mixed with about 1-60% glass reinforcement at the glass level to increase strength, stiffness, creep resistance and deformation resistance at high temperatures and to reduce the coefficient of thermal expansion. be able to. The compatibility of the new imide polymers according to the invention with glass reinforcements is so high that glass reinforcements containing standard binders can now be used rather than specially prepared reinforcements. If necessary, the novel imide polymers according to the invention can be foamed.

Various foaming methods can be used in this case. For example, a chemical blowing agent is mixed with an imide polymer according to the invention, the polymer is plasticized under pressure in the cylinder of an injection molding machine, and the chemical blowing agent is decomposed and then rapidly fed into the mold recess. One method is to feed it into an injection molding machine. Various densities, e.g. about 0.4 to 1.2 evenings/
A product of cc can be obtained. The above-mentioned foam member has the advantages of being rigid, freely designable, soundproof, and resistant to corrosion. In another embodiment, glass fibers are added together with a chemical expansion agent to produce a foamed strength heat resistant member with an artistically beautiful surface and excellent chemical and strain strength. I can do it. Similarly, fillers such as trihydrated alumina can be added together with chemical swelling agents and pressed into flat sheets with various desirable properties such as low density, high bending modulus, and flame resistance. You can also take it out. The extruder is preferably of a multi-screw type, such as a twin-screw counter-rotating extruder or a two-screw interlocking co-rotating extruder.

The products according to the invention are novel and possess various properties not possessed by conventional imide polymers.

That is, it has high tensile and flexural strength, resistance to solvents and hydrolysis, thermal stability, high working temperatures, good optical properties, weather resistance, barrier properties and other properties. The polymer according to the invention has no crosslinks.

The above polymer is dimethyl formamide (DMF)
This is clear from the fact that it dissolves in Having a uniform molecular weight and a uniform imide content are particularly desirable properties of the polymers according to the invention and are not achievable by conventional methods.

More specifically, most polymer molecules have the same imide content, so that the composition has a narrowly controlled compositional configuration. The molecular weight of these compositions is the same as or very close to that of the starting acrylic acid polymer.

This is also a great advantage compared to conventional methods which lead to a reduction in molecular weight. From a chemical point of view, the composition according to the invention consists of a thermoplastic polymer containing imide units having the chemical formula:

In the formula, R,, R2 and R3 each represent hydrogen or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an allyl group, an alkaryl group or an aralkyl group.

R. and R2 are derived from acrylic or methacrylic esters and R3 is derived from ammonia or primary amines or mixtures thereof. In the case of 100% imidized polymers, the glutarimide structure is essentially the only repeating unit, but in the case of lower degrees of imidization, in addition to the glutarimide units, there are also acrylic units having the following chemical formula: exist.

In the formula, R4 represents a lower alkyl group or another group derived from a half ester of an acrylic unit.

When acrylic units are present, the ratio between imide units and acrylic units is usually about 1:9 to about 9:1, preferably about 3:4 to 4:3.

Most preferred are imides derived from ammonia.

Therefore, R3 is preferably hydrogen. Preferably, the acrylic acid polymer is a homopolymer of methyl methacrylate. The polymer according to the present invention can be used for taillight lenses,
Used as molding powder, pellets, or granules to make toys, watch glasses, and various other molded products.

Similarly, the above-mentioned assembly can be in the form of a sheet, a cassette, a tube, etc. The composition according to the invention can also be used as an oil additive, since it has good viscosity properties such that it does not become viscous at low temperatures, but becomes a viscous oil at higher temperatures. .

The imide polymers according to the invention do not have any obtrusive odor when prepared under favorable conditions and are not processed by injection molding, extrusion, milling or other polymer processing methods. It does not produce any unpleasant odor.

Even at temperatures of 400 qo or higher, polymerization decomposition that releases ammonia or amines does not occur.

The thermal stability of the polymers according to the invention is one of the most significant advantages when compared with similar polymers of the related art.

As a result of testing using thermogravimetry analysis, TGA as a test method, the polymer according to the present invention has a thermal stability to the extent that it loses 1% of its weight when heated to about 2860 °C in air. . The following examples are shown to illustrate the invention, but the invention is not limited thereto. All parts and percentages are by weight unless otherwise specified. The following abbreviations are used in the description below.

P -- polymer MMA-methyl methacrylate EMA-ethyl methacrylate EA-ethyl acrylate BA-butyl acrylate MA-methyl acrylate AA-acrylic acid MAN-metacrylic.

Nitrile E - Ethylene VA - Vinyl acetate DMF - Dimethylformamide MDC Monodichloride Methylene Examples 1 to 44 Feed port for introducing acrylic acid polymer in the form of granular, pellet or powdery solids and under high pressure an additional closure for introducing ammonia or a primary amine at
The cylindrical part has five separate regions of about 84 arcs each that are heated or cooled by oil, a die that serves as a discharge entrance for the polymer product, and a The acrylic acid polymers listed in Table 1 were introduced through a feed port into a dual counter-rotating extruder having a discharge port operated under vacuum.

The amine or ammonia reagents listed in Table 1 were introduced into the extruder body immediately after the stepless screw section (mixer).

The liquid mixer forms a vapor-tight seal that prevents the reagents from returning to the polymer feed port. While the above reagents are passed forward through the reaction zone under the pressures indicated in Table 1,
Contact and mix with the polymer. Unreacted reagents and volatile products and by-products in the reactor are removed from the outlet under vacuum. The imidized polymer product exits the extruder through the die in a molten, unfoamed form and substantially free of volatile materials. Examples 7-21
And the extruders used in Nos. 27 to 44 have two additional discharge ports.

The first outlet is maintained at high pressure by a restriction valve provided on the outlet, and the second outlet is maintained at atmospheric pressure. The above two outlets are provided after the amine introduction closure and before the vacuum entry point which is under negative pressure as shown in Table 1. The extruder used in Examples Matsu-26 was the same as that of Examples 7-21 and 27-44, except that it had third and fourth additional outlets located before the amine introduction closure. The extruder used is the same.

The third outlet is under atmospheric pressure and the fourth outlet is under vacuum. In Table 1, the degree of imidization is expressed as %nitrogen (%N
) and the following base polymers are used.

AI. 15 [ri] skin F pMMA B The weight ratio of the polymer is 94/4, [sword].

p(MMA/EA)C 96/4 with NF 0.80
So, [ri].

Mp is 0.55 p(MMA/EA)D [sword]o
pMMAE [ri] whose MF is 1.35.

pMMAF (95/15) with MF of 0.80 and p(MMA/EA) with owp of 1.65
G Syrup consisting of 50% A and 50% MMA monomers 60% B and 85/15 proportions MMA and EA
Syrup 1 consisting of 40% mixture with pMMAJ 75/25/25 with an oMp of 2.7,
the law of nature〕.

p(EMA/BA/MA)K 5 where MF is 0.51
p(MMA/BA)L with a ratio of 0/50 and [ri]oNF of 0.80 [ri]oMF with a ratio of 95/5
p(side A/M) where is 1.05 is a ratio of 90/10, and p(side A/M where owF is 0.70)
N is the ratio of spots/2, [ri].

p side A/M state where MF is 1.35) 0 80/20
p(MMA/
VA) P is a ratio of 75/25, and Moc is 0.
．． p(MMA/E)R which is 45 and p(MMA/E)R whose MDc is 0.57 in the ratio of 75/25.
[ri] oMF is 1.05 (pMMA) S 50/
p(MMA
/EA)T [ri]oMF is 3.0 pMA U 80/20 ratio, [ri]Moc is 1.0 p(MMA/E)V [ri]oMF is 0.64 p
MMAW 95/5 ratio, oMF is 0.76
p(MMA/BA)

This is indicated by writing the example number under the "Supplies" column in the table. Table 1 Table 1 (Continued) Example 45 Although the shape is different, Examples 1 to 3 have a polymer supply port, a high pressure opening, an amamine supply port, an atmospheric pressure entrance, a vacuum entrance, and a discharge die. In the same extrusion reactor used up to 44, base polymer A was imidized under the same conditions as in Example 7, resulting in a nitrogen content of 1.5% and an IR
The bond in Svectra meant the formation of an imide group.

Example 46: A copolymer of MMA and EA in a ratio of 7 to 30 with an oMp of 2.7 was prepared at a rate of 2724/hour on a two-axis counter-rotating cutting line with an axis diameter of 51.4. It was supplied to the supply port of the extruder.

The polymer was carried downwards to the barrel, where it melted and then passed through a restricted area which served as a pressure seal. With respect to the movement of gases, there are 2 parts in the chest of the extruder, where the diameter of the barrel, which is isolated from the rest of the extruder, is 1&n;
Ammonia was added at a rate of 72.4k9/hr.
The ammonia is added to the downstream entrance of the reaction zone, and unreacted ammonia and reaction products exit the reaction zone from the upstream end of the reaction zone. The flow of vapor is thus in a reactive direction relative to the flow of polymer. The pressure in the reaction zone is 33
．． Maintained at 42 atmospheres. The polymer passes from the reaction zone to the outlet zone under atmospheric pressure in which most of the remaining methanol and ammonia are removed.

The polymer is conveyed into a discharge area operating under reduced pressure to aid in the removal of the last remaining traces of ammonia and methanol. The polymer is then extruded through a multi-hole die and out of the extruder. Many fibers formed in this way are 2 female 4k
9/hour to give the final product. The above product has a nitrogen content of 9.0% and a V of 200
It has a softening point of icat. The product does not dissolve in boiling water nor is it attacked by mild acids or salts. The molecular weight of the product is within 10% of the molecular weight of the starting polymer. Example 47 In the extruder described in Example 46, the skin F was 0.84.
A copolymer of 96% methyl methacrylate and 4% ethyl acrylate is introduced at a rate of 1430 k9/h.

The polymer is solidified, melted, and formed into a continuous stream of molten plastic that is propelled through the extruder. Through the use of stepless and counter-step bells, the extruder is divided into regions through which polymer can flow but steam cannot pass.
A pressure difference of more than 68 atmospheres can be created between these two regions without passing steam. Anhydrous monomethylamine is added to the "reaction" zone of the extruder at a rate of 7 paper kg/hour. The above substances are gaseous under the conditions under which the extrusion operation is carried out. The mo/methylamine gas and molten polymer are brought into intimate contact by several intensive mixing shaft sections in the reaction zone. A portion of the amine dissolves in the molten polymer. The molten amine reacts with the ester units in the polymer, displacing methanol and forming a 6-member moated imide ring attached to the polymer backbone. Excess amine and ethanol reaction product in the form of vapor are removed out of the extruder through an outlet located at the end of the reaction zone. The pressure in the reaction area is maintained at 4 atmospheric pressures by the pressure regulating valve provided at the discharge port. A molten polymer containing molten monomethylamine and methanol is propelled into an outlet region operating at atmospheric pressure. In this region, most of the molten amine and methanol are removed. The polymer is then fed into the entrance area where it is subjected to a pressure of 0.06 atmospheres. Here the remaining molten amine and alcohol are removed. The molten polymer, thus freed of volatiles, is extruded through the die and forms a number of fibers as it is extruded from the extruder. These fibers are continuously cooled and cut to form a polymer product in the form of a molded powder of 1195 k9/hr. The extruder is heated such that the entire area of its barrel is maintained at 280°C. However, only the first supply area is maintained at 150°C. The material collected from the three outlets recovers the majority of the monomethylamine in pure form for sending back to the reaction zone.
It is processed in such a way that a methanol solution containing some monomethylamine is recovered. The above solution is also used in several commercial applications in such a way as to produce monomethylamine by reacting ammonia and methanol. The polymer produced by the method of the invention has an oMF of 0.76.

The reduction in molecular weight upon imidization is due to weight loss due to chemical changes in the side chains and not due to any significant reduction in the length of the polymer backbone. The polymer according to the invention has a Vicat softening point of 18〆○, as measured by ASTM D1525-70.

The polymer is transparent and colorless and can be processed using all conventional techniques used to make useful articles from thermoplastics. ASTM D-256-
56, this polymer has a weight of 7.5 ft. −
lbs. It has a sill pea non-notched impact strength of . Example 48 Wership rPneiderer twin screw intermeshing, extruder,
pMMA at a rate of 50 min/min during type ZDS-L28
Add.

Methylamine is added at a rate of 10 min/min under 170 atmospheres to an inlet near the feed end of the extrusion apparatus. Unreacted methylamine and volatile products are removed out of the extrusion apparatus through a vacuum outlet near the die end of the extruder.
The resulting polymer had a nitrogen content of 8.4% and an IR
Subectra revealed that it was essentially all imide. EXAMPLE Add pMMA to a 491 inch Killion single screw extruder at a rate of 50#/min.

Ammonia is added to the inlet near the feed end of the extrusion device at a rate of 8 minutes/minute. Unreacted ammonia and reaction products are removed from a vacuum outlet near the front end of the extruder. The resulting product is a clear and colorless polymer soluble in DMF. Example 50-1 (Comparison) A Additional test of Example 7 of West German Patent DAS No. 1077872.

According to the description in the patent, an aqueous ammonia solution (NH3 to day20 ratio of 80/2 by weight) was fed at a rate of 5 cc/min through a single-shaft outlet plug, and a pMMA solution (ratio of NH3 to day 20 of 80/2 by weight) was supplied at a rate of 40 cc/min. sp/c; 0.5).

The extrusion equipment was a 1 inch Killion with a 24/1 1/d and a 1/2 inch by 2 inch outlet at 60% of the distance from the feed to the die. The outlet had a plug with an inlet, which was connected by a steel line to a LAPPLS-5 pump, which was connected to a feed cylinder. The extruder was operated at 100 RPM, with an arm temperature of 265°C. If a first shaft is used that has a groove narrowing from 0.255 to 0.110 mm (from the outlet area toward the die),
The highest pressure of ammonia that could be produced was 15 atmospheres. This is because the above pressure seemed to be leaking out through the die. In an attempt to obtain the pressure specified in the patent, the 'a} polymer feed rate was increased to 70 min/min, but the ammonia pressure remained at 15 atm. 'b} When the ammonia feed rate was increased to 11 cc/min, the ammonia pressure increased to 2 p atm, but the air pressure seemed to completely escape through the die. . In an attempt to achieve the pressure conditions described in the above-mentioned patent, a second ball having a narrow groove of 0.200 to 0.050 and a screen pack were used,
The ammonia supply shed speed was set at 5 cc/min.

However, this time too, pressure leaked from the polymer supply V supply gate,
Apparently, only 15 atmospheres of ammonia pressure could be obtained. However, the die pressure was 5 aerobic pressures. Therefore, the measured pressure described in the above patent was considered to have been measured at this location. To keep the device running, pMM
A had to be forcibly supplied. I tried increasing the ammonia feed rate to 10 cc/min, but the pressure did not increase. Although Example 7 of the above-mentioned patent was repeated and various attempts were made, imidization was not observed in any of the cases.

Example 51 - (Comparative) In accordance with the present invention, a 0.8 inch welder's two-bag extruder having the configuration described in Examples 1-6 is used, with the rear tendon of the shaft having an arrangement starvation; Heat to 260 o - 270 o'clock and use non-aqueous ammonia.

We attempted complete imidization of NF=M5pMMA. 0
．． A near-vacuum pressure of 9 to 0.001 atm was applied to the vacuum outlet.

A smooth, continuous fiber product was obtained from the extruder.

The product did not need to be dried and could be further processed without intermediate steps. There was no ammonia outlet open to the atmosphere and all by-products could be removed. The product was poly(glutarimide). The thermal stability of this product was tested by dynamic thermogravimetry analysis (TGA). The results are shown in Table 2. B. To demonstrate the critical importance that the amine must be water-insoluble and that the pressure applied to at least one outlet must be below atmospheric pressure,
A comparative experiment was conducted under the same conditions. In this case, however,
Ammonia water (weight ratio of NH3 to Nippon 20 is 80 to 20)
was used to close the vacuum outlet.

The product extruded from the extruder in this case was a discrete, foamed mass propelled at high velocity by ammonia pressure and blocked by a shield located approximately 4 feet from the extruder die. A large amount of ammonia was expelled from the die into the air. The above product is ground into a fine powder;
It had to be dried. The product was vacuum dried at 120° C. for 1 hour and tested for thermal stability by dynamic TGA. The results are shown in Table 2. Both the products produced according to the invention (A) above and the products produced according to comparative experiment B had the same degree of imidization (100%) and equal melt viscosities, whereas the products produced according to the comparative experiment The product exhibited significantly lower thermal stability than similar products of the invention.

The results shown in Table 2 show that at a typical processing temperature of about 300 oo, product A loses only about 1% of its weight, while product B loses more than 2% of its weight. It shows. The above difference may be due to the fact that one product has a smooth surface without bubbles, whereas the other has a rough surface containing bubbles.
Table 2 Thermal stability dynamic TGA, temperature increase rate 20 °C/min loss Temperature of air or (mass) nitrogen when all forces are lost °C Air Nitrogen A B A B 1 285100 300105 2 370175 400275 3 385350 440385 4 395380 420405 5 400390 420410 Note-A-Product B-Comparative Experimental Product Example 52 In this example, Graves U.S. Pat.
No. 6209 and U.S. Patent No. 3 to Schr6 der et al.
A comparison was made between a polymer made according to the method of No. 284425 and a polymer made according to the present invention.

The polymers made according to Examples 1 and 0 of the A GRAVES patent are likely polymethacrylimides.

However, according to the above examples, the polymer actually produced was soluble in dilute ammonia and boiling methanol. The polyglutarimide polymers according to the invention are insoluble in dilute ammonia and also in boiling methanol. The product produced by the GVE patent appears to be a polymer of methacrylimide, methacrylamide, and ammonium methacrylate.

B SCHRODER et al. In order to compare the autoclave, 12 Abe's 331
/3% methylamine aqueous solution and 78 liters of water together with 12 liters of polymethyl methacrylate at 230 qo.
heated for an hour.

A suction pressure was generated. The reaction product is separated from the aqueous phase by 32.
7 parts of solid polymer. The solid polymer was washed with water and analyzed and found to contain 8.5 soil and 0.2% nitrogen content. The above 32.7 parts corresponds to 34.6% of the initially supplied amount. The results of a comparison of the polymer made according to the Schr8der patent with the polymethyl methacrylate/methylamiso reaction product made in an extruder according to the present invention are shown in Table 3. The data in Table 3 shows that compared to the polymer produced according to the present invention, S
The polymer of Chr6der et al. clearly shows poor thermal stability.

The Schr6der et al. polymer exhibits a weak and ill-defined glass transition temperature compared to the polymer according to the invention. The Schr8der et al. polymers also begin to soften at lower temperatures (DTUFL and Vicat). Sch
The translucent nature of the R8der et al. polymers appears to indicate non-uniform imide levels when compared to the transparent or homogeneous nature of the polymers according to the invention. The difference in water resistance is Schr8
The properties of the polymer of Der et al. are shown to be inferior to those of the polymer of the present invention. Example 53 6.5 parts of the poly(glutarimide) polymer prepared according to Example 18 was mixed with M old S prepared according to Example 1 of U.S. Pat. No. 3,985,704, filed June 19, 1979.
Mixed with 3.5 parts of impact modifier and added with 0.5% by weight of antioxidant, 460 ml of
Processed at temperatures between o and 5100F to produce opaque fibers.

The opaque fibers were pelleted, dried at 90 pm, and cast at extrusion temperature. The polymeric polymer prepared as described above has a Vicat of 185°C and 18
0 (66psi), 160 (264psi) and 17
DTUFL (00) of 0 (264 psj phosphorous state)
It had The above product weighs 1.1 ft. ” bs. It had a Han's Izod notch impact strength, a 4 x 1 tensile coefficient, and a tensile strength of 9 x 1 psi at failure. Example 54 Using an impact modifier prepared according to Example 1 of U.S. Pat. No. 3,808,18, the ratio of imide to the modifier was
Similar results were obtained when the same composition as in Example 4 was used, except that the ratio was 2:2 and 1:1.

Excellent balanced properties were obtained by using the above impact modifiers in place of MBS and A mottling modifiers. Example 55 Using the same composition as in Example 53, except that the ratio of M old S modifier to poly(glutarimide) was 6 parts to 4 parts, a translucent product with the following properties was gotten.

Vicat135qo: DTUFL120q0 (66p
si), 100q0 (2 rat psi); Izod notch impact strength, 2.9 t. -1. /in, tensile system number 3×
Tensile breaking strength 6 x lpipsi. Example 5
6 1 part polycarbonate instead of 1 part polyglutarimide
The polymer was prepared in the same manner as in Example 53, except that 50% of the polymer was used, and an opaque polymer mixture having the following properties was obtained.

Vicat170℃; DTUFL170q0 (66ps
i), 13500 (2Mpsi), 14500 (264
psi, annealed), Notched Isot impact strength 2.1 ft. -lbs. Han, tensile system number 3 × 1 'p
si, tensile breaking strength, 7×1 and psi. Example 57
5. For every $ part of polyglutarimide, 4.1 parts of impact modifier was used, and the following chemical formula was used instead of MBS impact modifier: Bd/St〆MMA〆St〆MMA/
A polymer was produced in the same manner as in Example $ using one of the compounds represented by AN/St; 71/3〆3〆11〆4/4/4.

The properties of the resulting mixture are as follows.

Vicat160℃: DTUFL147℃, (66ps
i), 140°C (264 psi), notched isot impact strength 1.8 t. -lbs. /in; tensile system number 3×1
Tensile breaking strength: 8 x 1 pipsi. Table 3 Autoclave extruder test (sgohadara R) (invention) Yabu Nishishi 0
．． 2 85 83・Intrinsic viscosity Melt ratio Flow condition C O. 45 1.
0DMF insoluble 0.3
59585DMF Formic acid 0.24
020 Tetrahydrofuran Undissolved Dissolved Vicat temperature °C 170 177 DTUFL on balloon °C 90 122 Tensile impact (average of 5 measurements, variation 20.7
13.4 Large (unreliable) tensile test Tensile breaking strength, psi 12,800 12,
loo tensile system psi 519,000 5
18, ooo Increase in bush weight after 35 hours when placed in boiling water 5.2 3.
3 Surface condition Very hazy Good optical properties Opaque/white Transparent yellow Original optical properties Translucent gray Transparent/yellow Original differential thermal analysis (
DTA) Dislocation properties Weak and unclear Sharp and clear Dislocation temperature 194 179 Temperature gravimeter analysis (TGA) 1 Tortoise weight loss (air) ℃ 240
3651 Inferior weight loss (N2) ℃ 245
3953 Blind weight loss (air) ℃ 360
3953*Weight loss (N2)℃ 395 4
Embodiments of the present invention will be described below as test results for determining the presence or absence of at least one amine group by nuclear magnetic resonance analysis conducted using the 103.14d signal.

m substantially anhydrous ammonia or primary amine in about 1
3. A process for producing a polymer containing imide units according to claim 2, characterized in that the polymer is introduced through an additional closure of an extruder under a pressure of from atmospheric pressure to 100 pressures.

{21 The method for producing a polymer containing imide units according to claim 2, wherein the sand has an average residence time of 0.1 to 100.

'3} The method for producing a polymer containing imide units according to claim 2, wherein the degree of imidization is adjusted by controlling the average residence time and temperature.

{4' The method for producing a polymer containing imide units according to claim 2, wherein the temperature is about 300 to 375 qo.

'5' Claim 2 characterized in that no solvent is used.
A method for producing a polymer containing an imide unit as described in 2.

'6- The method for producing a polymer containing imide units according to claim 2, characterized in that no catalyst is used.

[7] Anhydrous ammonia is introduced through the extruder attachment closure under a pressure of about 1 atm to 500 atm, maintaining an average residence time of 3 seconds to 30 seconds, and at least one outlet has a pressure of about 0. Production of a polymer containing imide units according to claim 2, characterized in that the reaction is carried out in the absence of a solvent by applying a partial pressure of 9 to 0.01, maintaining the temperature at about 325 ° C. to 375 qo. Method.

'81 The method for producing a polymer containing imide units according to claim 2, characterized in that a partial pressure of about 0.9 to 0.01 atm is applied to the discharge port.

(2) A composition comprising a polymer product containing imide units produced by the method according to claim 2.

00 The composition according to item 9, which is in the form of a sheet, a camphor, a tube, a powder, a granule, or a molded product.

(11) The composition according to item 9, wherein the polymer is a multilayer polymer containing imide units in its outer layer.

(12) The acrylic acid polymer is a mixture of a single layer polymer and a multilayer polymer, and the polymer containing imide units is a single layer polymer and a multilayer polymer containing imide units in the outer layer thereof. The composition according to item 9 above.

(13) The composition according to item 12, characterized in that the composition comprises a mixture of about 10 to 60% by weight of the multilayer polymer containing imide units.

(The polymer containing 1 imide unit is about 0.01 to 7.0
10. The composition according to item 9, which has an intrinsic viscosity of oMF.

(15) The composition according to item 9, wherein the polymer containing imide units further contains acrylic units, and the ratio of imide units to acrylic units is from about 1:2 to about 9:1.

(16) The composition according to item 9, wherein 95 to 100% of the polymer units are imide.

07) The composition according to item 9, wherein 1 to 35% of the polymer units are imide.

(The composition according to item 9 above, wherein 1 further contains an impact modifier.

(19) The composition according to item 18 above, wherein the impact modifier is a multilayer polymer.

(20) The composition according to item 19 above, wherein the impact modifier is selected from the group of MBS, A spots and all acrylics.

(21) The composition according to claim 1, further comprising an impact modifier. (22) The composition according to item 21 above, wherein the impact modifier is a multilayer polymer.

(23) The composition according to item 21 above, characterized in that it contains an impact modifier selected from the group consisting of MDS, ABS, and all acrylics.

2. The composition according to claim 1, wherein the above thermoplastic polymer is a multi-layer polymer containing units represented by the above chemical formula in its outer layer.

(25) Claim 1 comprising a mixture of a single-layer thermoplastic polymer containing imide units represented by the above chemical formula and a multilayer polymer containing imide units represented by the above chemical formula on its outer skin. Composition of.

(26) The composition as described in 26 above, wherein the multilayer polymer comprises a mixture of about 10 to 60% by weight.

(27) The composition according to claim 1, wherein the thermoplastic polymer further contains units selected from other ethylenically unsaturated monomers.

(28) The thermoplastic polymer has a weight of about 0.1 to 7.0.

The composition according to claim 1, characterized in that it has a cape-like intrinsic viscosity. (29) The composition according to claim 1, which is soluble in tetrahydrofuran and dimethyl sulfoxide.

(3) The composition according to claim 1, which is in the form of a sheet, rod, tube, powder, granule or molded product.

(31) Claim 1, characterized in that the polymer containing imide units further contains acrylic units, and the ratio of imide units to acrylic units is from about 1:2 to about 9:1. Composition of.

(32) The composition according to claim 1, wherein 95 to 100% of the polymer units are imides.

(33) The composition according to claim 1, wherein 1 to 35% of the polymer units are imides.

Claims (1)

[Scope of Claims] 1. A thermoplastic polymer or copolymer containing a unit derived from acrylic acid or methacrylic acid or an ester thereof, wherein the thermoplastic polymer has a structural formula ▲ mathematical formula, There are chemical formulas, tables, etc.▼ (In the formula, R_1, R_2, R_3 are hydrogen or carbon number 1
-20 substituted or unsubstituted alkyl, allyl, aralkyl or alkaryl groups or mixtures thereof);
0%, and the polymer has no cross-linking and is soluble in dimethylformamide, and the temperature at which the polymer decomposes by 1% is at least about 285°C in thermal stability as measured by TGA in air. A thermoplastic polymer composition with high thermal stability and melt flowability. 2 The acrylic acid polymer and ammonia or primary amine are heated in an extruder under substantially anhydrous conditions at about 200°C.
There are structural formulas, ▲mathematical formulas, chemical formulas, tables, etc.▼ (in the formula R_1 , R_2, R_3 are hydrogen or carbon number 1
-20 substituted or unsubstituted alkyl, allyl, aralkyl or alkaryl groups or mixtures thereof);
An imidized acrylic acid polymer composition, wherein the polymer has no cross-linking and is soluble in dimethyl formamide, and the temperature at which the polymer decomposes by 1% in thermal stability as measured by TGA in air is at least about 285°C. How things are manufactured.