SE442122B - COMPOSITION BASED ON IMIDIZED THERMOPLAST POLYMES AND USE THEREOF - Google Patents

Description

15 '50 8201738-5. 2 or more, in the presence of an inert solvent or suspending solvent. U.S. Patent No. 3,557,070 discloses a process for preparing ethylene / methacrylic acid / methacrylamide terpolymers from an ethylene isopropyl methacrylate copolymer by heating the copolymer to the decomposition temperature of the isopropyl ester (325 ° C) to form methacrylic anhydride units which are then reacted with to form methacrylaxnide and methacrylic acid residues in the polymer chain. The reaction proceeds without solvent and in the example of the patent specification decomposition "zones" are mentioned. Although this patent does not mention that these reactions take place in an extruder, the Derwent abstract of this patent mentions that the reactions can be carried out in an extruder. The use of extruders such as polymer reactors has been shown as a route to copolyesters (Preparation and Properties of copolyesters Polymerized in a vented extruder, J. Applied Polymer Science, 12, 2ü03 (1963)), nylon products (Direct Extrusion of Nylon Product from Lactams, Modern Plastics, August 1969 - Werner Pfleiderer) and for graft polymerization of polyolefins (U.S. Pat. No. 3,862,265). West German Patent 1,077,872 discloses an extrusion process for imidizing acrylic polymers using an aqueous solution of ammonia, but the product is a foamed strand with poorer thermal stability and it requires further treatment before it can be used to produce useful products; in addition, the process described is not commercially suitable in that the foamed polymer starts from the extruder under high pressure with free ammonia vapor. It has been found that polymers, especially acrylic or methacrylic polymers, (can be oxidized in one of the Swedish 7612921-2, which uses short residence times and which allows continuous operation and control of the degree of imidization without significant deterioration of the molecular weight. Polymers can be obtained which are substantially completely and / or uniformly imidized and which exhibit a desirable balance of properties, such as high and even molecular weight, improved thermal stability, thermoplasticity and lack of bridging.

In addition, according to this procedure, the degree of imidization is controlled so that less than complete imidization can be achieved.

This new process involves reacting the polymer with ammonia or a primary amine in an extruder under substantially anhydrous conditions, as defined below, at a temperature of from 200 to 40 ° C, while applying subatmospheric pressure to at least an air valve opening in the extruder.

F, f Es this L * - f »10 30 n) kf! Generally, the polymer to be imidized is derived from at least one acrylic and / or methacrylic monomer, preferably at least one acrylic and / or methacrylic acid ester. The polymer may contain units derived from one or more other ethylenically unsaturated monomers such as acrylic acid, methacrylic acid, acrylonitrile, styrene, ethylene and butadiene, but of course the polymer must contain units with groups which can be imidized.

The polymer may comprise a single-step polymer and / or a multi-step polymer whose outer steps contain groups which can be imidized.

Usually the polymer contains at least 24% by weight, preferably at least 50% by weight, especially more than 80%, and most preferably 95 to 100% by weight, of this ester. Preferred are those in which the ester moiety contains 1 to 20 carbon atoms, most preferably methyl methacrylate (MMA) due to its low cost and availability. Polymers of monomer systems comprising at least 80% by weight of MMA are very suitable.

The polymer can have a molecular weight within a wide range. Since commercially available acrylic polymers exhibit an intrinsic viscosity in dimethylformamide, [n] DMF; of from about 0.01 and up to about 7.0 or higher, these are preferred. Acrylic polymers with an [n] DMF of about 0.28 to 2.0 are most preferred.

M Often the starting materials comprise a single-stage polymer, dry or molten, mixed with a multi-stage impact modifier, in which case the single-stage polymer and primarily the outer stage of the multi-stage polymer are imidized. Such blends are more compatible than blends of the imidized one-step polymer with the same multi-step polymer, especially when the latter is not imidized. Preferred are blends of single-step acrylic polymers with about 10 to 60 weight percent multi-step polymer.

The acrylic polymer may be in any form but it is usually in the form of a compression stock or in granular form, and may be colorless or colored, but in some cases the imidization process affects the dyes or pigments, and in such a case the dye is incorporated after the treatment.

Ammonia or primary amine is preferably a compound of the formula RBNHQ wherein R 3 is hydrogen or substituted or unsubstituted alkyl or aryl having up to 20 carbon atoms.

Mainly anhydrous ammonia or primary amine, or mixtures thereof, are introduced into the reaction zone in gaseous or liquid form under pressure, but in the case of primary amines it can be introduced in solid form. Due to their readiness for availability, ammonia and methylamine are mainly preferred by compounds of the formula RSNH2, _ _ _._..- «- q ~ w _.-., -> ...-..... V _? Û ÜÅÉ. 'Q Urine; 1. .IL Uï Ö 8201738-5 4 but also other compounds work well in the process and also provide highly desirable products. Other suitable amines include, for example, ethyl, n-propyl, n-butyl, heptyl, hexyl, octyl, nonyl, decyl, dodecyl, hexadecyl, octadecyl, isobutyl, sec-butyl, t-butyl, isopropyl, 2-ethyl, hexyl , phenethyl, allyl, alanine, benzyl, parachlorobenzyl and dimethoxyphenethylamines, alanine; glycine; 3'-aminoacetophenone; 2-aminoanthraquinone; and p-aminobenzoic acid. Also cyclohexylamine, 2-amino-α, 6-dimethylpyridine, 5-aminophthalimide, 2-aminopyrimidine, 2-aminopyridine, 2-aminothiazole, 5-amino-1H-tetrazole, aniline, bromaniline, dibromaniline, tribromaniline, chloroaniline, chloroaniline, trichloroaniline, p-phenetidine and p-toluidine are suitable. It is important that little or no water is introduced with said ammonia or primary amine, never more than 2 wt-1, preferably less than 1 Z, based on ammonia or primary amine. In the present context, the term 'mainly water' is defined by the previously mentioned maximum water contents. According to the new process, the polymer is fed continuously to an extruder and ammonia or primary amine is introduced continuously at the same time, usually via an injection port. Undesirable by-products and excess ammonia or primary amine are removed by progressively reducing the pressure at downstream air valves in the machine, leaving at least one downstream air valve under vacuum (subatmospheric pressure). Sometimes only one air valve under vacuum is sufficient to adequately remove all by-products and unreacted ammonia or primary amine. Preferably, a partial pressure of from 0.9 to 0.01 atmospheres is applied to this valve opening.

The temperature in the extruder can be varied, depending on the nature of the starting materials, pressure, residence time, etc., but is particularly dependent on the melt viscosity of the polymer being sprayed.

Usually a temperature of about 300 to 375 ° C is suitable, but about 200 to U50 ° C are usually the outer limits of the internal temperature of the extruder. Different sections of the extruder reactor can be maintained at different temperatures.

Preferably, the extruder is of the type with several feed screws, for example a twin-screw, tangential and counter-rotating extruder or a twin-screw engaging and co-rotating extruder.

A pressure as high as possible is preferred, but the most suitable pressure again depends on other factors such as. equipment limitations¿_You can work at such a low pressure as atmospheric pressure and q-u-a. .a ~ ... r. i .. .. ......- .. _ .. t .. 10 15 20 25 30 35 H0 5, 0 8201738-5 even a pressure as high as 1000 atmospheres is possible. In most embodiments, a pressure lower than 500 atmospheres is appropriate. When the primary amine is introduced in solid form, it may be introduced as a dry mixture with the polymer instead of through a separate addition port.

The reaction time (or average residence time in the reaction zone) is about 0.1 to 1000 seconds, preferably about 30 to 300 seconds.

The degree of imidization of the acrylic polymer can be easily controlled for the different properties of the process, and different degrees are selected as desired in the final product. The desired degree can always be achieved by adjusting reaction parameters such as residence time and temperature. Although a degree of imidization as low as 1 l can be achieved, at least 10 2 is usually required for an observable improvement in the property of the acrylic polymer. Up to about 100 Z of imidization can be easily achieved according to the process, which means that substantially all of the ester units in the acrylic polymer are converted to glutarimide units.

The process does not require catalyst. This results in the great advantage that necessary removal of catalyst is eliminated.

However, small amounts of catalyst increase the production rates.

Solvent is not necessary and it is preferred not to use one.

Preferably, the process is one in which anhydrous ammonia is introduced through the addition port of the extruder at a pressure of from 1 to 500 atmospheres, the average residence time being maintained at 30 to 300 seconds, a partial pressure of about 0.9 to 0.01 being applied to at least one air valve port, the temperature maintained at 325 to 375 ° C and the reaction is carried out in the absence of solvent.

The product leaves the extruder in molten form, and at this point other additives such as fibers, dyes and flame retardants can be incorporated. Optionally, additives such as, for example, impact modifiers, pigments, fibers, stabilizers, lubricants, etc. can be added to the polymer before introduction into the reactor.

The product can then be allowed to solidify in any desired shape e.g. such as sheet, hose, film, rod or strand, and the solidified product can be divided into powder or granular form as desired.

The product of the process may exhibit properties which have not been achievable with previous imide polymers, and more particularly include high tensile and flexural strength, resistance to solvent and hydrolysis, thermal stability, high operating temperature, good optical properties, weather resistance, barrier properties and other properties.

The imidized polymers are non-crosslinked, and this is shown by the solubility in dimethylformamide (DMF).

The uniformity of molecular weight and imide content of the imidized polymers is a particularly desirable property which usually cannot be achieved by prior methods. More specifically, most polymer molecules have the same imide content and the compositions thus have a narrow and controlled composition distribution.

The molecular weight of these compositions is the same as, or very close to, that of the starting acrylic polymer, which is also a great advantage over previous processes in which deterioration of the molecular weight occurred.

More specifically, according to the invention, there is provided a composition based on a thermoplastic polymer, the essential units of which are imide units with structural properties n 53 ° \ C / N \ c / ° É å '--c c-cH _- \ / 2 ef, CH2 1 \\ R2. wherein R 1, R 2 and R 3 represent hydrogen or C 1 to C 20 unsubstituted or substituted alkyl, aryl, which polymer is further characterized in that it is not crosslinked and is soluble in dimethylformamide and exhibits a degree of thermal stability , measured according to thermogravimetric analysis in an air atmosphere, which is such that the temperature at which the polymer has a decomposition of 1% by weight is at least 2 ° C.

The composition may contain a single-step polymer containing mother imide units and / or a multi-step polymer, the outer steps of which contain these imide units. Preferably, the composition comprising a mixture of the two types of polymer has a ratio of from H0 to 90% by weight of one-step polymer and from 10 to 60% by weight of multi-step polymer. The imidized polymer may contain other moieties derived from one or more ethylenically unsaturated monomers such as acrylic or methacrylic esters, acrylic or methacrylic acid, acrylonitrile, styrene, ethylene and butadiene.

However, the polymer is preferably derived from one or more acrylic and / or methacrylic esters, and when these polymers are in a formamide of from 0.1 to 7.0. The glutarimide structure is essentially the only repeating unit, but in the case of lower degrees of imidization, in addition to the glutarimide units, acrylic units of the formula coon "--e - cn2- H1 wherein H5 is lower alkyl or other radicals derived from the ester moiety of the acrylic moiety, are present.

When acrylic units are present, the ratio of imide units to acrylic units is usually from about 1: 9 to about 9: 1, preferably 1: 2 to -9: 1, most preferably about 3 = H to 11 u = 3.

The ammonia-derived imides are most preferred, which is why H3 preferably means hydrogen. The acrylic polymer is preferably a homopolymer of methyl methacrylate. Also preferred are polymers in which 95-100 Z of the polymer units are imidized and those in which 1 to 35 liters of the polymer units are imidized.

The thermoplastic polymer has an intrinsic viscosity in dimethyl. The polymer may also be soluble in tetrahydrofuran and in dimethyl sulfoxide.

The impact modifiers of the type ABS (acrylonitrile / butadiene / styrene), MBS (methyl methacrylate / butadiene / styrene) and of the total acrylic type have been found to be useful for improving the impact strength of the imide polymers while maintaining a high operating temperature. The ratio of impact modifier to imide polymer can vary over a wide range, depending on the degree of impact modification required for the application in question.

Ratios of impact modifier to imide polymer of from about 1:99 to about 70:30 are useful, and the preferred range is between about 5:95 and 60:40. The impact modifiers may be single step or multi-step polymers.

When multistage polymers are used, the impact modifier may exhibit a hard or soft first or "core" step followed by steps of varying hardness or softness. Examples of impact modifiers are those described in U.S. Patent Application 588,544, filed. June 19, 1975 and in U.S. Pat. No. 3,807,180.

The imide polymers used according to the invention do not have a significant odor when produced under preferred conditions, and can be produced by injection molding, extrusion, rolling or any other polymer processing process without odor or deterioration. - ring. Even at temperatures higher than 100 ° C, polymer decomposition occurs with the release of ammonia or amine.

The thermal stability of the polymers used according to the invention is one of the most distinctive advantages of the materials, compared to analogous polymers of the prior art. Thus, by thermogravimetric analysis, TGA, as the test method, the polymers exhibit. such a degree of thermal stability that the temperature at which the polymers exhibit a weight loss of 1% is at least 285 ° C in air, as shown in the example below, which corresponds to at least 30,000 in nitrogen for the particular polymer tested therein.

'A' Dynamic thermogravimetric analysis, (TGA), is as used in the present description, a standard test performed with a programmed temperature rise rate of 2000 / min in either air or nitrogen atmosphere on a duPont thermogravimetric analysis apparatus in combination with a differential thermal analysis device, as described in the duPont Instrument Products Division Preliminary Product Bulletin, 950-1 (A-36l77) - p “,.

Various aids can be added to the imidized polymer. For example, from about 0.1 to about 25% by weight of flame retardants may be used, preferably compounds of bromine, chlorine, antimony, phosphorus aluminum trihydrate; certain organic compounds containing two or more hydroxyl groups or mixtures thereof. More specific examples of flame retardants are triphenyl phosphate, phosphonium bromide, phosphonium oxide, tris (di-bromopropyl) phosphate, cycloaliphatic chlorides, chlorinated polyethylene, antimony oxide, ammonium polyphosphate, decabromodiphenyl ether and chlorinated polyphosphonate. The high use temperature of poly (glutarimide) in its base resin allows the addition of larger amounts of fire-curing agent than can be added to other base resins, while maintaining acceptable working temperature.

A wide variety of fillers can be used with contents of these fillers from about 5 to 80%. Surprisingly large amounts of fillers, such as e.g. hydrated alumina, can be mixed with the glutaramide polymer base resin, up to about 60 to 70%, while maintaining thermal formability. On the other hand, most thermoplastic systems can not receive more than about U0% inert filler while maintaining thermal formability. The imide polymers can be blended with glass reinforcement at glass levels of about 1 to 60% in order to increase strength, stiffness, creep resistance and resistance to deformation at high temperatures and to reduce the coefficient of thermal expansion. Compatibility of glass reinforcement with ,,. . im a - frT -1- K '(í fi, -; ü¿'¿§2.a__ g, fšääwe * i * 15 20 50 35 40 9 8201738-5 the imide polymers are unusually high and often allow the use of glass reinforcement, which exhibit standard type coupling agents instead of specially made reinforcements.

If desired, the imide polymers can be foamed. Several methods of foaming are used, e.g. chemical blowing agents are mixed with the imide polymer and fed to an injection molding machine, which softens the polymer and decomposes the blowing agent under pressure in the cylinder of the injection molding machine, followed by rapid feeding to the mold cavity. Goods with different densities, for example about 0.4 to 1.2 g / cmš, can be obtained. Such foam has advantages in terms of rigidity, freedom of design, acoustic damping and corrosion resistance. In other embodiments, glass fibers can be added together with chemical blowing agents to form a foamed, strong and heat-resistant part with an aesthetically pleasing surface and excellent resistance to chemicals and corrosion. Also fillers, such as alumina trihydrate, can be included with the chemical blowing agent and, for example, sprayed into a flat sheet with a number of desirable properties, such as lower density, good flexural modulus and flame resistance.

The composition according to the invention is useful as a press compound, pills or granules for the production of shaped products, such as lenses for taillights, toys, crystals in watches, to name just a few examples. The composition may also be in the form of sheets, rods or tubes.

According to another aspect of the invention, it thus relates to the use of the composition for the manufacture of products in the form of sheets, rods, tubes, powders, granules or shaped parts.

The composition according to the invention can also be used as an oil additive due to its good viscosity properties, and this composition does not increase the viscosity at low temperatures but thickens the oil at higher temperatures.

Thus, with a composition of the present invention, one can provide a synthetic or natural oil having dissolved or dispersed imidized polymer therein as previously described.

Some preferred embodiments of the invention are described in more detail below in and through the following embodiments, in which all parts and percentages are by weight and temperatures are given in OC, unless otherwise indicated.

In the working examples the following abbreviations were used: p = polymer of EA = ethyl acrylate MMA = methyl methacrylate BA = butyl acrylate EMA = ethyl methacrylate MA = methyl acrylate POOR CQ-Uåïlifïif UI 20 25 50 k »kn '... ~ .1 ....- 8201758- AA = acrylic acid É-MAN = methacrylonitrile E = ethylene VA = vinyl acetate DMF = dimethylformamide MDC '= methylene dichloride Examples 1 to H5 In a counter-rotating twin-screw extruder equipped with a feed opening for insertion of acrylic polymer in solid form, eg . such as granules, pellets or powders, an auxiliary port for introducing ammonia or primary amine at elevated pressure, a cylinder heated or cooled with oil in five separate zones, each about bra cm, a nozzle, which serves as a starting port for polymer into the product, as well as an air valve opening operating under vacuum and located in the last zone, the acrylic polymer specified in Table I is introduced via the feed opening.

Amine or ammonia reagents, listed in Table I, are introduced into the syringe cylinder just after a non-volatile compounder, which forms a vapor seal which prevents the reagent from being returned to the feed port of the polymer. The reagent is contacted with and mixed with the polymer as it advances through the reaction zone under pressure, as set forth in Table I. Unreacted reagent as well as the volatile products and by-products from the reactor are removed under vacuum at the valve. The imidized polymer product. ~ ._ ... v fl- nwï. .rwn -... m .... starts from the extruder through the nozzle in molten form, not foamed, and substantially free of volatile materials.

The extruder used in Examples 7 to 21 and 27 to H5 comprises two additional air openings, the first maintaining high pressure by means of a throttle valve and the second maintaining atmospheric pressure, and these air openings are located after the inlet opening for amine but before the vacuum opening , which is at ß the negative pressure given in Table I. '1 The extruder used according to examples 22 to 26 is the same as that in examples 7 to 21 and 27 to H5, except that it contains third and fourth additional air vents, located? before the amine introduction port, the third air port being at T at atmospheric pressure and the fourth at vacuum.

Table I indicates the degree of imidization of% nitrogen (% N) and the following base polymers are used: »owned ësé-» e-e- lo V En. \ $ l 15 20 25 ll 82Û1758 ~ 5 A. pMMA med [n] DMF ¿1,15.

B. p (MMA / EA), in a weight ratio of 96 / U in the polymer, and with [n] DMF = 0.80.

C. p (MMA / EA), 96 / Ü, and with [p] DMF = 0.55.

D. pMMA with [n] DMF = 1.35. pMMA [n] DMF = 0.80.

F. p (MM1 / EA), (95/15), {n1DMF = 1.65.

A syrup of 50% A "or 50% MMA monomer.

A syrup of 60% B with UO% of a monomer mixture of MMA and EA in a ratio of 85/15. pMMA with [n] DMF = 2.7. p (EMA / BA / MA), 75/25/25 and 1n] DMF = 0.51. p (MMA / BA), 50/50, {n] DMF = 0.80. , L. p (MMA / AA), 95/5, [n] DMF = 1.05.

M. p (MMA / MAN), 90/10, [n] DMF g 0.70.

N. p (MM1 / MAN), 98/2 and [n] DM æ, 1.35. 0. p (MMA / VA), 80/20, [n] DMF ä 0.51.

P. p (MMA / E), 75/25, [fi] MDC- = 0, u5. _ 0. pgmmß / a), 75/25, [nlm 9_, s7.

R. (PMMA), [f fl DMF = 1.05- s. P (MMA / EA), 50/50, but [fi] DMF = 0.61.

T. pMA, {fi] DMF = 3.0. u. p (MMA / E), 80/20, [n] MDC = 1.0.

V- PMMA, [δ nm = 0.611. 'w- pmMA / Bm. 95/5, DÜDMF = 0.76.

X. 50/50 mixture of I and V.

In some examples, the product prepared according to another example is introduced as feed material; this is indicated by entering this example number in the table under "feeding material". 110012 Q '“z11: = 1 = 1 a. 6. - ~ - .- ~ ....... .__ .v-ÄMAL ... _.- __. .... ~ 12 8201738 = ~ 5 NOH ON.N OH.O OON NH »HH.> = NH = _ ON m OH NNH OO.N OH.O ONN mHm HN.m = NH = NH m HH HOH ON «> OH ~ O ONN OHH O> .m = Hm = OH m NH = mH HN.O OH.O OON mHn = O.Hn On = NH N NH NHH Nm.m OH.O OON OH» = O.Hm NH = NH m HH ONH mmam OH.O OON .OOH OH.NH OH = Om N OH OO.m OH.O .OON OOH HO.ON O = NO ON Oæ.N OHHO OON OO »H0.0N O ._ O ON NO NN.H OH.O OON Oom .HH.mN O HNOOE »OON Ébnåmx 30 .HuLNwHHQ OMH: OQO OH.O OH» OOH OqmN O = Hm m O OOH ßmqm ONQO OHM OOH N.HO. N = Nm H m NOH ON.n HNQO OH »OOH> .OH N = HN <H ONH Nmnm OHQO OHM OmH = .om N = ON N O NOH OH fl m OHQO OH» OmH H.mm N = Hm H. N: HH> H.H OHHO OHM OmH ONON N HNHOOEEN HN O H Sum o; . cHE \ w Eum .namn n «E \> mm> _ c fi E \ w» mn Hm fi s o zw: wwc fi cnmm: Hwumë mswc fl xmæë _...._ ... »ms ... w fl pmms .f ... Háwvms nu a .èssåš mcmww _ nunnan OÉÉB ... wwpmms ... Hws nwwc fl: Hmš mumøuxsucnm ... U xvän. uc fi í fl ø: mcmnuw: c fi š nc fi ä fl .ÉENHHÉ .LHHom »sms ssøxm H AAMMFH. _ _ - ~~ »v -... F -... h 82817158-5 13 æm fi O fl. O o N o fl n oow>. = N od fl hows w = m om ow fi nn oH.o o fi n oom fi. Mm m fi xm fi coesm wa m mm mo fl wo o fi. o o fi n mom = .o ~ ma fi hxwso fi xho om m: N ow fl fl, ~ oH.o o fi n omm o. = mm Hæows om m mm mm fi Nm oH.o o fi n omm o.nm o fl = om m NN som Hß fi om.m o fl. o o fi n mm = oo.æm o = oz o fi m HJH @ fi. ~ nH.o o fl m om: ßm.om om = om o om oo fi = z. = nH.o o fi n om: m =. = mm = om o m fl oom mo.> m ~ .o o fi m .mmm @ =. = m flfifl = om o w fi mm fi: m.> o ~ .o o fl m mon o> .mm N = ow o »H = oH fl o.mn ~ .o oon men mo. ~ m N xm fi nøaem mm m od Eo \ mx xown» »w> m U: fl E \ w _Eom .name: fi E \> nm> n« E \ w sm: fl mwn o za cmwswcmam a fl wøm fi mcwcwxmm fi »mn nwwuwms cwuws ne B | E: sxm> mcnwu: vanan xoænv iwvmms ahwë Imwcwc fi mm mumuaxsoonm w xoznß acw n | fi n z nw v n z nw. QUAHTY lä 8201738-5 oom oom mm: msm fifi oo mmm XMMCOEEM & m »Q mnmcocmmn om mm: omm mmm mm mmmooasm om x _ :: 2 cmmmcm omm omm mm | nomx flfi v mm mn: omm omm N: Hmmm mm wm: mmm oom mm momsnfz om 3 H: omm oo: om Tnoomoomm oom> o: mmm mmm m m mmäšomxmo. o: o mm omm oom N fl mm fl oxz om B wn omm omm om s fl mcm om m mm omm oom om mmowooo oom m mm mmm mmm m xmmoossm om o mm omm omm m ü fi ws om m: m omm omm m. xmmoosem om o mm omm m5 .m .ï fi ms o: z mm omm oom .om xmmoosem om z mm mmm oom m i fi ws mm .m om omm _, oo: om xmmcossm oom m mm omm. omm m Hšmš mm m om oom omm m mmmnoesm om H mm o: mE \> nm>: ms \ w: mE \ w .mëwu fl mwwë mcmc fi xmmë uwswmmm: vmsm fi umms Hm fl nwumë hc msamocmmmo zusnmmmcwsum me | | mEww m <m .m @ hOmv H Aqmmdà o l5 20 30 HO _... ... min __ l .., .___ n .... ~ _.. -.-_..._- _ 15 8201758-5 R Example Gel 46 In an extruder reactor according to Examples 1 to H5, except for a used configuration of supplied polymeric material / high pressure orifice fed amine material / atmospheric pressure orifice / vacuum orifice inlet nozzle, base polymer A is imidized under the same conditions as in Example 7. nitrogen content of 1.5% and bonds in its IR spectra indicating the formation of imide groupsf Exemgel H7 27214 kg / nim of a copolymer of 70.30 MMA / EA with [f fl DMF = 2.7 fed to the supply neck of a twin-screw counter-rotating tangential extruder with a auger diameter of 5l, Ä cm. The polymer is passed down the cylinder, fluxed and then passed through a choke section which acts as a pressure seal. In a section of the spray cylinder, with a length of 15 times the diameter of the cylinder, and which is insulated with respect to gas transfer from the rest of the machine, ammonia is supplied at a rate of 272 .mu.g / h. Ammonia is fed into a downstream opening of the reaction zone and unreacted ammonia in and the reaction products start from the reaction zone at the upstream end of this zone 9. The steam stream thus flows in countercurrent to the polymer stream. The pressure in the reaction zone is maintained at 33.32 ° F atmospheres.

The polymer passes from the reaction zone to an opening zone at atmospheric pressure; in this zone the majority of the remaining methanol and ammonia are removed. The polymer is then passed into a; §§§§i§gš§§§: fš§ fi: §§§§ take under reduced pressure, to assist in the removal of the last residues of ammonia and methanol. The polymer then leaves the extruder via a multi-hole die. The many strands thus formed are cut to give 208U kg / h of final product. This product has a nitrogen content of 9.0% and a Vicat softening point of 200 ° C. It is insoluble in boiling water and is not attacked by weak acids or bases. The molecular weight of the product is in the range of 10 l of the starting polymer. Example Gel # 8 In an extruder, described in Example H7, a copolymer of 96% methyl methacrylate with U% ethyl acrylate with [n] DMF = 0.8H is introduced at 1330 kg / h. This polymer is compressed, melted and formed into a continuous stream of plastic melt which is propelled along the syringe barrel. By using non-volatile and inverted volatile screw sections, the machine is divided into zones through which the polymer can flow but through which the vapors cannot pass; Pressure differences of more than 68 atmospheres can be established between the zones without steam transport between these zones PQQR QUš-'lïiTíTï 20 25 39 35 H0 8201738-5. The "reaction" zone of this extruder is added to 738 kg / h of anhydrous monomethylamine, this material is a gas under the conditions of the spraying process. The monomethylamine gas and the polymer melt are brought into intimate contact by means of several intensive mixing screw zones in the reaction zone. The dissolved amine then reacts with the starch moieties in the polymer to replace methanol to form cyclic seximide rings attached to the polymer backbone.The excess amine and methanol reaction product are removed in vapor phase from the machine at an orifice located at the end of the reaction zone. pressure regulating valve at this opening establishes a pressure of UH atm in the reaction zone.The polymer melt, which contains dissolved monomethylamine and methanol, is propelled in an opening zone driven at atmospheric pressure.In this zone the main amount of dissolved amine and methanol is removed.Then the polymer passes into an opening zone under a pressure of 0.06 atm. In this zone, re stone of dissolved amine and alcohol. The polymer melt, which is then free of volatile materials, is forced through a nozzle to form several strands of polymer, which are expelled from the machine. These strands are continuously cooled and cut to give 1195 gk / h of the product polymer in molding composition. The extruder is heated in order to maintain the temperature of the syringe barrel in all zones at 28000, except for the first feed zone, which is maintained at 15000. The material collected from the three open gaps is treated in such a way as to extract most of the monomethylamine in pure form. for reintroduction in the cycle to the reaction zone, and a solution of methanol with a small amount of monomethylamine therein. There are several commercial uses for such a solution, such as for the production of monomethylamine by reaction between ammonia and methanol.

The polymer prepared according to this process has [n] DMF = 0.76. The decrease in molecular weight upon imidation is due to the weight loss resulting from chemical conversion of the side chains and is not due to a significant reduction in the length of the polymer backbone.

This polymer has a Vicat softening point of 18200 measured according to ASTM D1 525-70. It is clear and colorless and can be processed with all normal techniques, which are used to produce valuable products from thermoplastic materials. The polymer has an impact strength without Charpy instruction of 1.0 kpm measured according to ASTM 11-256-56. Exemgel H9 _ Polymer MA at a speed of 50 g / min is added to an engaging extruder type ZDS-L 28 with double feed screw of brand l5 20 F.) “JI 30 35 HO 17 szo fi vßs-5 Werner Pfleiderer. To an injection port, near the feed end of this machine, methylamide is added at a rate of 10 g / min at 170 atm.

Unreacted methylamine and volatile products are removed from the machine at a vacuum opening near the nozzle end of the machine. The resulting polymer has a nitrogen content of 8, U 5 and gives an IR spectrum, which shows that the polymer near consists entirely of imide.

EELIPLIÅQ pMMA at a rate of 50 g / min is added to a 1 "Killion single screw extruder. To this machine is added ammonia at a rate of 8 g / min at an inlet opening near the feed end of the machine. Unreacted ammonia and reaction products are removed near a vacuum opening of a machine end. The resulting product is a clear and colorless polymer, soluble in DMF.

Example 51 (comparative control example) A. Try to repeat Example 7 according to the West German script DAS 1,077,872.

As in the reference, an aqueous ammonia solution (NH 3 / H 2 O ratio of 80/20 by weight) was introduced through an air hole plug into a single screw at a rate of 5 cm 3 / min, to a feed of HO g / min of pMMA (n SP / C = 0.5). The machine was a 1 "Killion with a 1 / d of 2% / 1 and an opening of 1/2" x 2 "located at 60 l of the distance from the feed to the nozzle, the opening being provided with a lid with an inlet opening, which in turn was connected, by means of a steel line, to a LAPP LS ~ 5 pump, which in turn was connected to a feed cylinder.The machine operated at 100 in 3. .-. Wade-nun rpm with a cylinder temperature of 265 ° C .

With a first feed screw with a channel width reduction from 0.255 to 0.110 (seen from the opening area to the nozzle), the highest possible achievable ammonia pressure was 15 atm, since the pressure seemed to be vented via the nozzle. Attempts were made to achieve the pressure given according to this reference, whereby (a) the feed rate of the polymer was increased to 70 g / min but the ammonia pressure remained at 15 atm, (b) the ammonia velocity was increased to 11 cm / h with the resulting ammonia pressure increase to 20 atm, but the pressure still seemed to be vented through the nozzle.

In an attempt to achieve the pressure conditions reported in the reference, a second feed screw was used with a channel width reduction from 0.200 to 0.051, a filter pack and an ammonia speed of 5 cm / min, but again an ammonia pressure of 15 atm could be achieved, as the pressure seemed to be vented by polymer feed port.

However, the pressure of the nozzle was 50 atm, which may indicate that it was here the pressure was measured according to the reference. The polymer MMA must be forcibly fed to keep the system running. The ammonia rate was increased to 10 cm 3 / min, but the pressure was not increased.

No imidization was observed in any of these attempts to repeat Example 7 according to the reference.

Example 52 (Comparative Control) A. According to the invention, a 0.8 "twin screw extruder of the Welding Engineers type having the structure described in Examples 1-6 was used to completely imidize a pMMA with [n] DMF = 1.65 with non-aqueous ammonia under a pressure of 55 atm and a temperature of 260-27000 and at a point, located about 1/3 of the length downwards along the feed screw.A vacuum of 0.9 to 0.001 is applied to the vacuum opening.

'An even and continuous product string emanates from the extruder. The product does not require drying, and it can be further processed without intermediate steps. Ammonia openings to the environment are not required and all by-products are chambered. §_ The product is po1y (glutarimide) and is tested for thermal stability by dynamic thermogravimetric analysis method (TGA); * with results reported in Table II. §§ B. In order to demonstrate the critical importance that the amine lf is non-aqueous and that subatmospheric pressure is applied to at least one opening, a comparative experiment was carried out using the same conditions as in A above, but using aqueous ammonia. (in a NH3 / H2O ratio of 80/20 calculated on the weight), where-: - after the vacuum opening was plugged again. The product was based on the extruder which foamed discontinuous masses of ammonia pressure at high speed and was stopped by a screen mounted about 1.2 m from the nozzle of the machine. Large amounts of ammonia were aerated from the nozzle to the surroundings. The product was ground to a fine powder and then required drying. It was vacuum dried at 12,000 for 16 hours and tested for thermal stability by dynamic TGA, and the results obtained are reported in Table II. Although the products prepared according to the invention (A above) and according to this comparative experiment (B) showed equal degrees of imidization (100%) and equal melt viscosity; obtained in the comparative experiment a product which was considerably less thermally stable than the analogous product according to the invention. The results in Table II indicate that at normal processing temperatures, around about 30,000, product A loses only about 1% of its weight, while product B loses more than 2 ß. This difference can mean the difference between a product without bubbles having a smooth surface and a product with bubbles and rough _ F - '"i" --- ~ - ----..._ w' "“ T ¥ tai-å * ~ 10 15 20 25 19 TABLE II THERMAL STABILITY Dynamic TGA, Temperature increase rate 20 ° C / min. 8201738-5% w / v Temp. ° C. Air or nitrogen, at which the loss total weight loss is the specified Air Nitrogen A '' E å å 1 285 100 300 105 2 Bïü 175 UOO 275 3 385 350 HBO 385 l: 595 380 1120 1405 5 uoo 590 'lszo 1410 Note. : A represents the invention B is a comparative control experiment.

Examples 53 In this example, polymers prepared according to U.S. Patents 2,1H6,209 and 3,28H.U25 are compared to polymers of the invention.

A. U.S. Patent No. 2.1U6.209 The polymers prepared according to Examples I and II of this U.S. Patent Specification are believed to be polymethacrylimides. According to these. For example, the polymers prepared in fact are soluble in dilute ammonia and boiling methanol. The polyglutarimide polymers of the present invention are insoluble in dilute ammonia and insoluble in boiling methanol. The product of this U.S. patent appears to be a copolymer of methacrylimide, methacrylamide and ammonium methacrylate.

B. Autoclave of U.S. Pat. No. 3,28ü.U25 For Comparative Purposes Example 1 of this U.S. Patent is performed using 120 parts of polymethyl methacrylate heated for 7 hours at 250 ° C in a stirred Parr type autoclave with 129 parts 33 1/3 % aqueous solution of methylamine and 780 parts of water. 3 A pressure of Bl atm is developed. The reaction product comprises an aqueous phase and 32.7 parts of a solid polymer, which were washed and analyzed to give a nitrogen content of 8.5 to 0.2 5. These 52.7 parts represent 3fl, 6% of the original bet.

The polymer of this U.S. patent is compared to the polymethyl methacrylate methylamine reaction product prepared in the extruder of the present invention, whereby results reported in Table III were obtained.

These data show that the polymer of this U.S. patent is POÛIC. QUALITY! \) 1 20 30 55 HO ..f, - .. a ... - '-'_, - ~ ._ _ h ..- ..._. 8281758-5 20 3.28ß.H25 is clearly less thermally stable than the polymer prepared according to the present invention; the polymer of this patent has a weak, poorly defined glass transition temperature compared to the polymer of the invention and it begins to soften at a lower temperature (DTUFL and Vicat). The transparency of the material of this U.S. patent appears to indicate a non-uniform imide content, as compared to the transparent and thus uniform polymer of the invention. The difference in water resistance indicates inferior properties of the polymer prepared according to this American patent specification.

Example 54 6 l / 2 parts of poly (glutarimide) polymer prepared according to Example 18 are mixed with 5 l / 2 parts of MS impact modifier prepared according to Example 1 in U.S. Patent Application 588.5 μl of June 19, 1975, and 0.5% by weight of antioxidant at 238 266 ° C in a single-screw extruder equipped with an opening under vacuum in order to produce transparent strands, which are then formed into pellets, dried at 90 ° C and injection molded at injection temperatures. The polymer mixture produced had a vic value of 185 ° C, a DTUFL (° C) of 180 (δ, 6 kp / cm 2), 160 (18.56 kp / cm 2) and 170 (18.56 kp / cm 2 annealed). The product exhibited an impact strength according to Izod with an instruction of 0.06 kpm / cm and a tensile modulus of 2.8: x 10 xp / cmz and the tensile strength of 6.3 x 102 kp / cmz at break.

Compositions similar to those of Example 4, except for using the impact modifier of Example 1 of U.S. Pat. No. 3,808,180 with ratios of 3/2 and l / l modifiers, gave similar results.

Substitution of MBS and ABS modifiers gave excellent balance of properties, Example 56 A composition according to Example SÄ, except that the ratio of poly (glutarimide) to MBS modifiers of 6 parts to Ä parts, gave transparent products with the following properties: vicat 135 ° c; DTUFL 120 ° C (k, 6M xp / cm 2), 100 ° C (18.56 kp / cm 2); Izoà with instructions of 10, lÄ kpm / cm; tensile modulus 2.1 x 10 ”kp / cmz and tensile strength limit H, 2 x 102 kp / cmz.

Example 57 'Example SU was repeated except replacing some polyglutarimide with some polycarbonate to give opaque polymer blends having the following properties: 17 ° C; Mum, 17 ° C (01.614 kp / cm 2), 135% (1856 xp / CIIF), 1.5 ° C (18.56 kp / cm 2 annealed); Izod with instructions of 0.11 kpm / cm; tensile modulus 2.1 x 105 kp / cm? and tensile strength limit U, 9 kp / cmz.

Example 58 Example 53 was repeated except that 5.9 ae1a1-polyglutarimide was used in 14.1 parts of the impact phase modifier, and the impact modifier MBS was replaced by one of the following formulas: Bd / St // MMA // St / / MMA / An / St: 71/3 // 3 // ll // H / 4 / M.

The properties of the resulting mixture were as follows: vicat 16o ° c; DTUFL 1147 ° c 04.614 kp / cm2), 1uo ° c (18.56 kp / cmzn Izod with instructions of 0.08 kpm / cm; tensile modulus 2.1 X 10 kp / cmz; and tensile strength 5.6 x 102 kp / cmz. won Qïïë fi êïuffš 22 8203758-5 onmbnmam ohm> hmc .nmmnznwu fi ëm w | px fi> fl nwc fl ë> m onm> nm: nmwcm 6: ann ø «> Hmcw fl m> m anm> nw: .mæ cow mm w mcmm» Hn @@ px fi> wm om o pms fl vw: fl hmm »x fi> xm mmm m = ~ wo AANZV» w: fi »@@ px fl> & H mmm ozm U Apms fi v» w: Hnmm »x fi> x H ^ <øBw mæ fl mcm xw f m "mE f> mnwoEnwE MSS al: others L ser @ spmnwQEw @ mw: mmnw> m ømnw fi cwmw @ f m> mhmxw ømhm f n f UMV vw fifl mv wm> m nuscwmmmxmmn mcmwmmwhw> m H w \ mm fl x maw \ mw fi fi xwEo: mm nmmmxmswww mxm al umo mw flfi wzsnmmas fi: mm: w f \ nm f x @ f> \ xmQo nwnmxwcmww mxw al AEMO Gwß al häøm f ß nfHwxrm mv fifi d flfi mßäßu al ßwßn N w: xm »x«>. sm @ »m> mwsmxox« E f p mn nwpmm ozwm ommm s0 \ @x Hsøosxom fi pm iff com mëuwmx wsmnwvwomnwmmn = .mH Nnom ^ @@ hw> w = @@ fi @ = ° x »wm fi = @ w fi H» gßwH @@: Oo w = fi = nu fi mmm nova Uwe nmmcwcnæä m> mp @ fl: mEo: mwv wønm> mm fi w mm fi om oo ^ < 2av = øwHmwcs <.vosnm: pwoB = Q “w: w Q zam <pw fifi aw Aqmøaav wg fl spmm fi mn H fl zæ u fl> ew @. @ M ß> H oß fl Q n: @m fi maewp @ m0 «> w fifi wm fi w flfi ww fi o cmmsmohuæsmnum» fl ømno: mao æ »> w§> s \ m: nm \ m @ fl mn.o w fifi mm fi o man H on fl m: .o U no fi p fl so øsoo n: <.Hmm pwsw fi pwwnph fi up fl wsm uwp fi moxm fi> wcmaQ mw m fl w No H. @> W> xx, Acmwswcc fi maas .fl smv ^ mm =. = Æm.n .nxw.m; E c fl xmmeusnmwwcmnßm> maxh @ hmmm

Claims (13)

8201738-5 zs PATENTKRAY Composition for use in the manufacture of shaped products and as an oil additive, characterized in that it is based on a thermoplastic polymer, the essential units of which are imide units of the structural formula ïš O \\ C / “\ / ° c / CH - 7 "GHz" K 2 R1 32 wherein R1, R2 and R3 represent hydrogen or C1-C20 unsubstituted or substituted alkyl, aryl, which polymer is further characterized in that it is not crosslinked and is soluble in dimethylformamide and has a degree of thermal stability, measured by thermo-gravimetric analysis measured at a programmed temperature rise rate of ZOOC / min in an air atmosphere, which is such that the temperature at which the polymer has a 1% by weight decomposition is at least 285 ° C . Composition according to claim 1, characterized in that it comprises a single-step polymer containing said imide units and / or a multi-step polymer, wherein the polymer obtained in external steps contains said imide units. 3. A composition according to claim 2, characterized in that it comprises from 40 to 90% by weight of one-step polymer and from 10 to 60% by weight of multi-step polymer. 4. A composition according to any one of claims 1-3, characterized in that the polymer contains other units which are derived from one or more of acrylic acid esters, methacrylic acid esters, acrylic acid, methacrylic acid, acrylonitrile, styrene, ethylene and butadiene. Composition according to any one of Claims 1 to 4, characterized in that from 95 to 100% of the polymer units are imide units. Composition according to any one of Claims 1 to 4, characterized in that from 1 to 35% of the polymer units are unit units. A queue position according to any one of claims 1-6, characterized in that the polymer contains said imide units and units derived from at least one acrylic and / or methacrylic acid ester, the numerical ratio of imide units to __ - 1, ._. __ ~ _-aa. riPc) (§X {Å: É fi§ xi5ï¶ 8201738-5 24 acrylic and / or methacrylic units are from 1: 2 to 9: 1. 8. Know the viscosity of dimethylformamide of from 0.1 to 7.0. Composition according to any one of claims 1-7, in that the thermoplastic polymer has a limit 9. A composition according to any one of claims 1-8, characterized in that it is additionally soluble in tetrahydrofuran and dimethyl sulfoxide. 10. a composition according to any one of the claims. 11. A composition according to claim 10, characterized in that the impact modifier is a multi-stage polymer. Composition according to Claim 10 or 11, characterized in that the impact modifier comprises at least one of the type acrylonitrile / butadiene / styrene, methyl methacrylate / butadiene / styrene or acrylic resin only. Use of a composition according to any one of claims 1-12 for the manufacture of products in the form of sheets, rods, tubes, powders, granules or shaped parts.