AU509727B2 - Imidized polymer - Google Patents

Description

j_ (Forms 1 and 4 combined)

x CO MMONWEALTH OF AUSTRALIA

SPATENTS ACT 1952-1973

APPLICATION FOR A PATENT

'19 821 We ROHM AND HAAS COMPANY, a corporation organized f~"E rn--der law.v of the State of Delaware, United States of America, of Independence Mall West, Philadelphia, United States of America,

hereby apply for the grant of a Patent for an invention entitled:

"IMIDIZED POLYMERS"

which is described in the accompanying specification. complete

The application is a convention application and is based the application(s) for patent or similar protection made

United States of America 19th November, 1975 under No. 633,302

under No. APPLICATION ACCEPTED AND

ALLOWED

address for service is care of DAVIES COLLISON Our Patent Attorneys, of 1 Little Collins Street, Melbourne, in the State of Victoria, Commonwealth of Australia.

DATED this 18th day of November, 1976.

a e i

Cmber of the firm of DAVIES COLLISON) for and on behalf of the applicant To: Ir of Patents ROHM AND HAAS COMPANY

COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952-1973 DECLARATION IN SUPPORT OF CONVENTION OR NON-CONVENTION APPLICATION FOR A PATENT OR PATENT OF ADDITION In support of the Application made for a patent for2 aninenio for an inentio Insert title of tention. entitled: "IMIDI ZED POLYMERS"

Insert full name(s) and address(es) I KENNETH NORMAN RIMTNGTON, of 1 Little of deciarant(s) being the appli- cant(s) or person(s) authorized to Collins Street, Melbourne, Victoria 3000, sign on behalf of an applicant company.

Cross out whichever of paragraphs 1(a) or 1(b) does not apply do solemnly and sincerely declare as follows 1(a) relates to application made 1. FIhz apphL.nt fnh by individual(s) patent of additiza 1(b) relates to application made or I am authorized by ROHM AND HAAS COMPANY by company; insert name of applicant company.

the for the patnnt Cross out whichever of paragraphs 2(a) or 7(b) eoes not apply lmte~t to make o this declaration on. addticitheft- t behalf.

2(a) relates to al'plication made 2. 1 mo hivni by inventor(s) 2Jlq~pJ8e$ to application made or(b) RICHARD MICHAEL KOPCHIK, of 1335 Stephen Way, by*Lomnmny(s) or person(s) who are not Inventor(s); insert full Southampton, Pennsylvania 18966, United njitxl gnd addreveas) of inven- States of America, tos a a S

Saemne. i hc ppiats 's he actual inventor of the invention and the facts upon which the applicant deiv til frmivetrs is entitled to make the application are as follows

The said applicant is the assignee of the said actual inventor

bStates andinawich applicant(s).

3. The basic application as defined by Section 141 of the Act was made WeCC in United States of Ameril;the November, 1975 by RICHARD. MTCHEL dnerv tile from invenors)gaue in on by 19Q in on

4. The basic application referred to in paragraph 3 of this ecaat as the first application made isn a Convention country in respect of the invention the subject of the application. Declared at MEL80URNE this 18th day of November. 197 .A.6. Slgnatr- declarat(s) (no aWTimaso reqluired) Note: Initisi all alterations.

(11) AU-B1-19,821/76

(12) PATENT SPECIFICATION ABRIDGEMENT (19) AU

(21' 19,821/76 509,727 (22) 19.11.76 (23) 19.11.76 (24) 19.11.75 (31) 633,302 (32) 19.11.75 (33) US (43) 25,5.78 (44) 22.5.80 (51) 2 C08F 8/30 C08F 8/32 C08F 20/14 C08F 20/16 C08F 20/18 C08F 265/04 C08F 265/06 (54) Imidized polymer (71) Robin and Haas Company (72) Kopehik, R. M. (74) DM (56) 13,380/76 C08F (57) It is important that little or no watei e introduced with the ammonia or primary amine, never more than 2 percent by weight, preferably less than 1 percent, water based on ammonia or primary amine, for purposes of this invention, the term substantially anhydrous is defined by the afore- mentioned maximum water contents. Claim 1. A process for the imidization of an imidizable polymer which comprises reacting said polymer with ammonia or primary amine in an extruder under substantially anhN drous conditions, as hereinbefore defined, at a temperature of from 200 to 450 0 C. while applying subatmospheric pressure to at least one vent port of the extruder.

fr\ ND 18-7

4.

*f I ('U'lROtr r~ 972 I OR?.I

COMI'LLETE SI'lCI HCATION ((Jrigin,i) F011 OFFICI: LJS

]nf, Class

.Apfplication Numnlle Lodgucd

*..:Complete Spucilwatirors I It 1 'll At f f( l itII Ish (I

sectio ej made ~tin 0 :::Priori ty Qu49. U1a

R, elato(] At I 79 4tcr~Ct forprnig

ILI

Narnru of tpli'cdn ROHM AND HAAS COMPANY

Ad r s of*0l(: l

Independence Mall West, Philadelphia, United States of America,

AddIress lo Auilr.un RICHARD MICHAEL KGPCHIK

I I~jCuL~b. IStreet, Mclbouiiru, 3000

C01111fleto speciflcimiori lot Ihrv rrvrorrlror r~rrllIjt'r "IMIDIZED POLYMERS."

'he followIlng st erIMIrt t Is 111ll dr'st,tipil of t ins ii venirIon, rcindudiIrf 11w rustI IiethoUJ of jier formning it kn~on to US

S 509 727 This invention is concerned with imide polymers and

their preparation.

The formation of imides by reacting ammonia, butyl-

amine, dodecyl amine or octylamine with polymethyl meth-

acrylate is disclosed in Graves U.S. Patent 2,146,209, German

Patent 1,077,872 and German Patent 1,242,369. Schroder et

al U.S. Patent 3,284,425 and British Patent 926,629 disclose

a route toward imidized acrylics by reacting polymethyl meth-

acrylate with ammonium hydroxide, ammonium phosphate, alkyl

amines or a combination of partial reaction with ammonium

hydroxide followed by reaction with alkyl amine. British

Patent 1,045,229 discloses chemical modification of methacrylic

:acid/methacrylonitrile (MMA/MAN) copolymers or terpolymers

by heating at 180-300°C., to give the cyclic amide product,

optionally with a dispersing solvent. German Patents

1,247,517; 2,041,736 and 2,047,096 show methacrylamide/methyl

methacrylate (MACM/MMA) copolymers, inert solvent, and heat

to achieve imide formation accompanied by evolution of

ammonia. Most prior patents and literature on processes to

,e 20 imidized acrylics via reaction of ammonia and primary amines with polymethyl methacrylates, Patent 3,284,425 for o

example, are directed to an autoclave batch process requiring

lengthy heating time, usually 7 hours or more, in the presence

of inert dissolving or suspending solvent. U.S. Patent

3,557,070 describes a process for preparing ethylene/methacrylic

acid/methacrylamide terpolymers from an ethyleneisopropyl meth-

acrylate copolymer by heating the copolymer to the decompos-

ition temperature (325 0 of the isopropyl ester to form

'a -3-

methacrylic anhydride units which are then reacted with gas-

eous ammonia to give methacrylamide and methacrylic acid

residues in the polymer chain. The reaction is run neat

without solvent and the patent examples mention decomposition

"zones". Although this patent does not mention that these

reactions are taking place in an extruder, the Derwent ab-

stract of this patent mentioned that these reactions may be

run in an extruder. The use of extruders as polymer reactors

has been shown as a route to copolyesters (Preparation and S

10 Properties of Copolyesters Polymerized in a Vented Extruder, J. Applied Polymer Science 12,2403(1968), nylon products

S" (Direct Extrusion of Nylon Product from Lactams, Modern

Plastics, August 1.969 Warner Pfleiderer) and graft poly-

Smerization of polyolefins (Steinkamp et al U.S. 3,862,265).

West German Patent 1,077,872 discloses an extruder process

of imidizing acrylic polymers using a water solution of

ammonia, but the product is a foamed strand with deficient

thermal stability and which requires further processing I

before it can be used to fabricate useful items; furthermore, e 20 the process described is not commercially feasible in that

the foamed polymer exits the extruder under high pressure

with free ammonia vapor.

We have now found that polymers, especially acrylic

or methacrylic polymers, may be imidized in a process which

uses low residence times and which lends itself to continuous

operation and the control of the degree of imidization without

substantial molecular weight degradation. Polymers may be

provided which are substantially completely and/or uniformly imidized and which have a desirable balance of properties, such as high, uniform molecular weight, improved thermal stability, thermoplasticity and no crosslinking.

Moreove:-, the process of the invention may lend

itself to the control of the degree of imidization so that

less than complete imidization may be achieved.

According to the invention, there is provided a On Imi dcizob/e process for the imidization of/polymer which comprises

reacting said polymer with ammonia or a primary amine in an

extruder under substantially anhydrous conditions, as herein-

S. after defined, at a temperature of from 200 to 450°C. while

applying subatmospheric pressure to at least one vent port ar of the extruder. Preferably nro lly, the polymer to be imidized is derived

from at least one acrylic and/or methacrylic monomer,/prefer- S

ably 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, meth- *aa.

acrylic acid, acrylonitrile, styrene, ethylene and butadiene, 20 but of course, the polymer must contain units containing groups o capable of being imidized.

The polymer can comprise a single stage polymer and/

or a multi-stage polymer whose outer stage contains groups

capable of being imidized.

Generally the polymer contains at least 24 percent

by weight, preferably at least 50 percent by weight, more

preferably above 80 percent, and most preferably 95 to 100 per-

cent by weight of said ester. Preferred are the species wherein the ester moiety contains I to 20 carbon atoms, most preferably methyl methacrylate (MMA) due to its lower cost and availability. Polymers of monomer systems comprised of at least 80 percent by weight MMA are very suitable.

The polymer can have a molecular weight falling

within a wide range. Since commercially available acrylic

polymers have intrinsic viscosities in dimethyl formamide,

Lk I DMP, of from about 0.01 and up to about 7.0 and above, S these are preferred. Acrylic polymers having an ]DJI Lw of-abet 0.28 to 2.0 are most preferred. oS Frequently the starting materials will comprise a S. S

single stage polymer dry or melt blended with a multiple stage -Gios 0

impact modifier polymer, in which case the single stage poly-

mer and primarily the outer stage of the multiple stage poly-

mer are imidized. Such blends are more compatible than

blends of the imidized single stage polymer with the same

multiple stage polymer, especially when the latter is not

a imidized. Preferred are blends of single stage acrylic

polymers with abe;-t 10 to 60% by weight multiple stage poly- o* S mer. o55o5

The acrylic polymer can be in any form, but is

generally in molding powder or granule form, and can be

colorless or colored, but in some cases the imidization

process affects the dyes or pigments, in which case the

coloring agent is incorporated after processing.

The ammonia or primary amine is preferably a com-

pound of the formula R 3 NH 2 wherein R3 is hydrogen or sub-

stituted or unsubstituted alkyl or aryl having up to carbon atoms.

The substantially anhydrous ammonia or primary amine,

or mixtures thereof, is introduced to the reaction zone in

gaseous or liquid form under pressure, but in the case of

prima-y amines can optionally be introduced in solid form.

Due to ready availability, ammonia and methylamine are most

preferred of the compounds of the formula R 3 NH 2 but others

work very well in the process also, and also give very desir-

able products. Other suitable amines include, for example,

.0 ethyl, n-propyl, n-buty., heptyl, hexyl, octyl, nonyl, decyl,

S dodecyl, hexadecyl, octadecyl, isobutyl, sec-butyl, t-butyl, S

isopropyl, 2-ethyl hexyl, phenethyl, allyl, alanine, benzyl,

sc parachloro benzyl, and dimethoxy phenethyl amines; alanine;

glycine; 3'-aminoacetophenone; 2-aminoanthraquinone; and p-

aminobenzoic acid. Also cyclohexyl amine, 2-amino-4,6-dimethyl

pyridine, 3-amino phthalimide, 2-aminopyrimidine, 2-amino-

pyridine, 2-aminothiazole, 5-amino-l-H-tetrazole, aniline,

bromoaniline, dibromoaniline, tribromoaniline, chloroaniline,

dichloroaniline, trichloroaniline, p-phenetidine, and p-

20 toluidine are suitable. It is important that little or no

water be introduced with the ammonia or primary amine, never

9 more than ftbet 2 percent by weight, preferably less than. 1

percent, water based on ammonia or primary amine. For

purposes of this invention, the term substantially anhydrous

is defined by the aforementioned maximum water contents. preferr ec In accordance with the/preesos aspect of the inven-

tion, the polymer is continuously fed to an extruder, and the

ammonia or primary amine is introduced continuously at the same time, usually through an injection port. Unwanted by- products and excess ammonia or primary amine are removed by progressively reducing the pressure at downstream extruder vents, with at least one downstream vent at vacuum (sub- atmospheric pressure). Sometimes only one vent under vacuum is all that is necessary 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 the vent port.

The temperature in the extruder can be varied, de-

S pending on the nature of the starting materials, pressure,

o residence time, etc., but is especially dependent on the

melt viscosity of the polymer being extruded. Usually, about

300 to 375 0 C. is suitable, but ab-e-t 200 to 450eC./weli-d gea-

e-rally I the outer limits of the internal temperature of the

extruder. Different sections of the extruder-reactor can 5O

be maintained at different temperatures. S Preferably the extruder is a multiple screw type, for example a twin screw tangential counter-rotating extruder

or a twin screw intermeshing co-rotating extruder. *c S

As high a pressure as possible is preferred, but

again the pressure most suitable depends on other factors such

as equipment limitations. As low as atmospheric is operable, and as high as 1000 atmospheres is possible. In most embodi-

ments, below 500 atmospheres pressure is suitable. When

the primary amine is introduced in solid form, it can be in-

troduced as a dry blend with the polymer rather than through

a separate addition port.

The reaction time (or average residence time in the be- reaction zone)/ e-a~ett 0.1 to 1000 seconds, preferably about

to 300 seconds.

The degree of imidization of the acrylic polymer is

readily controllable in the process of the invention, and

different degrees are chosen for different properties

desired in the final product. The desired degree is con-

sistently achievable by adjustment of the reaction parameters

such as residence time and temperature. Although as low as

1% imidization can be achieved, at least 10% is usually 39 9 9 3 9 needed for noticeable property improvement of the acrylic 9 99 polymers. Up to about 100% imidization can readily be

achieved by the process, meaning essentially all of the ester

moieties of the acrylic polymer are converted to glutarimide

moieties. 9 .3,

9 No catalyst is necessary in the process. This

results in the great advantage of eliminating the necessity

of catalyst removal. Small amounts of catalyst conceivably

*99r... increase production rates, however. 9 No solvent is necessary, and it is preferred not to 0

6999c use any.

Preferably the process is one wherein anhydrous

ammonia is introduced through an extruder addition port at a

pressure of from 1 to 500 atmospheres, the average residence

time is maintained at 30 to 300 seconds, a partial pressure of ef/mo.Asheres eaout 0.9 to 0.01 is applied to at least one vent port, the

temperature is maintained at from 325 to 375 0 and the

reaction is conducted in the absence of solvent.

The product leaves the extruder in melt form, at

which oint other additives such as fibers, colors and flame

retardants can be incorporated. Optionally, additives such

as, for example, impact modifiers, pigments, fibers, stabil-

izers, lubricants, etc. can be added with the polymer prior

to introduction in the reactor. The product can then be

allowed to solidify in any desired form, sheet, tube,

film, rod or strand, and the solidified product can be chopped

into powder or granule form as desired. a The product of the process may have properties not a. possible with previous imide polymers, more specifically high a

tensile and flexural strength, solvent and hydrolysis resist- a

ance, thermal stability, high service temperature, good optical

properties, weatherability, barrier properties, and others.

The imidized polymers are non-crosslinked, and this a is evidenced by solubility in dimethyl formamide (DMF). a

The uniformity of molecular weight and imide content

of the imidized polymers is a particularly desirable property a generally not ach'evable in prior processes. More specific-

ally, most of the polymer molecules have the same imide o

*c 0 content, and so the compositions have a narrow, controlled

compcsition distribution.

The molecular weight of these compositions is the

same as or very close to that of the starting acrylic poly-

mer, which is also a great advantage as contrasted with prior

processes in which molecular weight degradation occurred.

B ;i

.I

The invention also provides compositions comprising

a thermoplastic polymer containing imide units of the

structural formula

OC N C 0

I C C CH 2 R CH R 1 2 2

5 wherein R 1 R 2 and R3 represent hydrogen or C1 to C20 unsub-

stituted or substituted alkyl, aryl, alkaryl, or aralkyl, R1 0 and R2 being preferably derived from the acrylic or methacrylic pre ero ly 00 acid esters, and R 3 /being derived from the ammonia or primary 0g

amine or mixtures thereof, the polymer being further character-

ized as non-crosslinke, soluble in dimethyl formamide and

having a degree of thermal stability as measured by thermo-

gravimetric analysis in an air atmosphere such that the temp-

erature at which said polymer has a 1% by weiht decomposition ort /east isae 28S0C.

The composition may comprise a single stage polymer

containing said imide units and/or a multi-stage polymer 0

whose outer stage contains said imide units. Preferably

compositions comprising a blend of the two types of polymer

S contain a ratio of from 40 to 90% by wei'ht of the single stage *9 05 00 polymer and from 10 to 60% by weight of the multi-stage poly- 4D mer.

The imidized polymer may contain other units derived

from one or more ethylenically unsaturated monomers such as

acrylic or methacrylic esters, acrylic or methacrylic acid, acrylonitrile, styrene, ethylene and butadiene.

Preferably, however, the polymer is derived from

one or more acrylic and/or methacrylic esters, and when such

polymers are 100% imidized 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

COOR 4 C -CH

R

wherein R4 is lower alkyl or other radicals derived from the 0*'

10 ester moiety of the acrylic unit w'ill be present.

When acrylic units are present, the ratio of imide

units to acrylic units is usually from abu-t 1:9 to abet 9:1,

preferably 1:2 to 9:1, and more preferably about 3:4 to 4:3.

The ammonia-derived imides are most preferred, and

15 so R 3 is preferably hydrogen. The acrylic polymer is pref- o0* erably a homopolymer of methyl methacrylate.

Also preferred are polymers wherein 95 100% of 5

the polymer units are imidized and those wherein 1 35% of

the polymer units are imidized.

The thermoplastic polymer may be characterized as

having an intrinsic viscosity in dimethyl formamide of from

0.1 to 7.0. The polymer may also be soluble in tetrahydro-

furan and in dimethyl sulfoxide.

Impact modifiers of the ABS (acrylonitrile/buta-

diene/styrene)/, MBS (methyl methacrylate/butadiene/styrene) Ay V

,Onrc aTx-rures of -i/esc 1yAes, all acrylic type/have been found to be useful for improving

the impact strength of the imide polymers while retaining

high service temperature. The ratio of impact modifier to

Simide polymer can be varied over a wide range, depending

upon how much impact modification is needed for the part-

icular- application. Ratios of impact modifier to imide

polymer of from abeut 1:99 to ftot-t 70:30 are useful, with

the preferred range being-abu-t 5:95 to 60:40. Impact mod-

0 ifiers can be single or multiple stage polymers. In the

o o 10 case of multiple stage polymers, the impact modifier can 9

4* have a hard or soft first or "core" stage followed by stages 9 9

6 S varying in hardness or softness. Exemplary impact modifiers 9 5 Spec,fjcc.ioi 3-T57o4 are those disclosed in U.S. Patent/Applitcion Z.N. 588,544 A)-lerlI cif;C 'cr -3'30',9 Junc 1D, 1975 ontitlod MS Craft Polymcrz and Proozso fe-r

Lhcir Production, and U.yS. Patont 3,808,180 of April 30, 197

S. The imide polymers of this invention do not have any r

9 0r significant odor when prepared under the preferred conditions, 0 and can be processed by injection molding, extruding, milling,

or any other polymer processing procedure without odor of 20 degradation. Even at temperatures of over 400°C., no poly- S. 29

meric decompositions so as to give off ammonia or amine takes

place.

The thermal stability of the polymers of the inven-

tion is one of the distinguishing advantages of the materials

as compared to analogous prior polymers. With thermogravi-

metric analysis, TGA, as the test method, the polymers of the

invention have a degree of thermal stabilit- wherein the

temperature at which the polymers have a 1% weight loss is at least 285°C in air which is shlwn in the Examples following to correspond to at least 300C in nitrogen for the particular polymer tested therein.

Dynamic thermogravimetric analycis, (TGA), as used

in this specification, is a standard test conducted with a

programmed temperature increase rate of 20 0 C./min. in either

QO an air or a nitrogen atmosphere on a duPont thermogravi- r metric analyzer in combination with a differential thermal

analyzer as described in duPont Instrument Products Division

Preliminary Product Bulletin 950-1 (A-36177).

Various adjuvants may be added to the imidized 6* polymer. For example, from 0.1 to 25 percent by o *o

weight flame retardant can be employed, preferably compounds *e Sof bromine, chlorine, antimony, phosphorus aluminum tri- 19. 15 hyd ate, 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-bromo propyl) phosphate,

cycloaliphatic chlorides, chlorinated polyethylene, antimony

20 oxide, ammonium polyphosphate, decabromo-diphenyl ether and I* chlorinated polyphosphonate. The high service temperature

of the poly (glutarimide) in its base resin permits larger

amounts of fire retardants to be added than can be added to

other base resins, while yet maintaining acceptable service

temperature.

A wide variety of fillers can be employed, at filler

levels of from 5 to 80 percent. Surprisingly large

amounts of filler such as hydrated alumina can be blended

1 with the glutaramide polymer base resin, up to 60 to

I4 70 perc-nt, while maintaining thermoformability. On the other hand, most thermoplastic systems cannot accept more than about 40 percent inert filler with retention of thermo- formability. The imide polymers can be blended with glass reinforcement at glass rvleels of -ena t 1 to 60 percent to enhance strength, stiffness, creep resistance and deform- ation resistance at high temperatures and to reduce the thermal expansion co-efficient. The compatibility of the glass reinforcement with the imide polymers is unusually high and frequently permits the use of glass reinforcement- which Sa a 10 has stancard coupling agents rather than specially prepared

0 6 reinforcements. '*one~ *O a a If desired, the imide polymers can be foamed. A

variety of methods of foaming can be used, for example chem-

0 ical blowing agents can )e mixed with the imide polymer and

fed to an injection molding machine which plasticizes the

*a *i polymer and decomposes the blowing agent under pressure in e dim Oer a, the cylinder of the injection molding machine with subsequent

rapid feeding to the cavity of the mold. Articles of variable S.. density, for example, sab;t 0.4 to g/cc, can be obtained. 0

Such foamed parts have advantages of rigidity, design freedom,

acoustic dampening, and corrosion resistance. In other

embodiments, glass fibers can be added along with a chemical

blowing agent so as to produce a foamed, strong, heat resist-

ant part with an aesthetically appealing surface and excellent

chemical and stain J.esistance. Also, fillers such as, for

example, alumina trihydrate can be included with chemical

blowing agent and, for example, extruded into flat sheet

having a variety of desirable properties such as lower density, good flexural modulus and flame resistance.

The imidized polymers of this invention have

utility as molding powders, pellets or grailes for use in

making molded articles such as tail light lenses, toys,

watch crystals, to name but a few examples. Also, the poly-

mer can be in The form of sheet, rod or tube.

The compositions of the invention can also be used

as oil additives due to good viscosity characteristics, not

adding to viscosity at low temperatures but thickening oil at

higher temperatures. S Thus, one embodiment of the invention provides a

synthetic or natural oil having dissolved or dispersed therein

imidized polymer as previously described.

Some preferred embodiments of the invention will now O O

be more partiGularly described in and by the following Examples oo0* in which all parts and percentages are by weight and all

temperatures are in unless otherwise specified.

t OO15 In the Examples the following abbreviations are used: 0 p_ polymer of

MMA methyl methacrylate

EMA ethyl methacrylate

EA ethyl acrylate

BA butyl acrylate

MA methyl acrylate

AA acrylic acid

MAN methacrylonitri2e

E ethylene

VA vinyl acetate

DMF dimethyl formamide

MDC methylene dichloride

EXAMPLES 1 to

In a twin screw counter-rotating extruder set up

with a feed port for introducing acrylic polymer in solid

form such as granule, pellet, or powder, an addition port

for introducing ammonia or primary amine at elevated pressure,

an extruder barrel heated or cooled with oil in five separate S

zones, each about 84 cm., a die which serves as the exit port

S* 10 for the polymer product, and a vent port operated under

vacuum and located in the last zone, acrylic polymer as speci-

fied in Table I is introduced via the feed port.

Amine or ammonia reagent, as specified in Table I,

i introduced in the extruder barrel just after a non-flighted

15 scr -;ction (compounder) which forms a vapor seal which

keeps the reagent from going back toward the polymer feed port.

The reagent contacts and mixes with the polymer as it moves

forward through the reaction zon,, under pressure as specified

in Table I. The unreacted reagent as well as the volatile

products and by-products of the reactor are removed under

vacuum at the vent. The imidized polymer product leaves the

extruder through the die in melt form, non-foamed, and essen-

r- tially free of volatile materials.

2 The extruder used for Examples 7 to 21 and 27 to

25 includes two additional vents, the first being a vent upon

which a high pressure is maintained by means of a restrictive

valve on the vent, the second being at-atmospheric pressure,

said vents being located after the amine introduction port but before the vacuum vent which is at the negative pressure specified in Table I.

The extruder used for Examples 22 to 26 is the

same as for Examples 7 to 21 and 27 to 45 except that it

includes third and fourth additional vents, located before

the amine introduction ports, the third being at atmospheric

pressure ndSth-s fourth being at vacuum.

In Table I, the degree of imidization is indicated

by nitrogen and the following base polymers are used:

.10 A. pMMA of DMF of 1.15. *0

B. p(MMA/EA), in a weight ratio of 96/4 in the

polymer, and of DMF 0.80. *o

C. p(MMA/EA), 96/4, and of DMF 0.55. S D. pMMA of I 1.35.

E. pMMA D, 0.80.

F. p(MMA/EA), (95/15), DMF 1.65.

G. A syrup of 50% A and 50% MMA monomer.

H. A syrup of 60% B with 40% of a monomer mixtures e of MMA and EA in a ratio of 85/15. 2 I. pMMA of DMF 2.7.

25 J. p(EMA/BA/MA), 75/25/25 and Jll DMF 0.51. K. p(MMA/BA), 50/50, DMF 0.80.

L. p(MMA/AA), 95/5, DMF 1.05.

M. p(lMA/MAN),90/10. l DMF 0.70.

S 25 N. p(MMA/MAN), 98/2 and WIZ DMF= 1.35.

0. p(MMA/VA), 80/20, J DMF 0.51.

D. p(MMA/E), 75/25, 1 MDC =0.45.

p'* 18

Q. p(MMA/E), 75/25, 0.57. R. (pMMA), l DMF 1.05.

S. p(MMA/EA), 50/50, of DD 0.64. T. pMA, DM DMF U. p(MMA/E), 80/20, J MD

V. pMMA, J DMF 0.64. W. p(MMA/BA), 95/5, tJ 0.76. X. 50/50 Blend of I and V.

In certain examples, the product produced in a 10 different Example is introduced as feed; this is indicated *9 o by entry in the Table of that Example number under "feed".

S

0

i,. 0

r. S e

S9

C. S see C C a. St S. C. S C 5 5 9 S. S S 5 OS 555 a 9 a S S S S. 0

TABLE I

Pressure Polymer Amine Amine Average in Vacuum Product Data Exampl e Rate Amine Rate Pressure Extru der Barrel Vent VI CAT No. Feed a/mn.- Type Q/mif. atm RPM TemD. 'C. atm w OC.

I G 27 Ammonia 7 29.9 15Q 3-10 0.-16 '1.47 134 2 1 3-1 it 7 35.4 -150 3-10 0.16 3.19 1-52 3 2 26 it 7 50.4 150 3-10 0.16 5.59 190 4 A 23 8 49.7 150 3-10 0.23 3.26 -157 4 32 a 61. 2 -150 310 0.26 6.57 '188 6 B 31 6 23.8 150 310 0. *16 0.74 -130 psia 67 Met-Ch /l 8 360 300 260 0.110 1. 22 f? 8 370 300 260 0. 16 2.86 62 8 370 300 260 0. 16 5.06 -175 360 280 0 -16 3.55 -126 49 '13 450 315 280 0.16 5.32 *142 47 30 450 315 280 0.16 6.81 -154 46 34 650 310 280 0.716 7.20 16,1 18 -12 700 315 280 0.16 8.00 '182 670 312 280 0.16 8.,20 '183

0@ 0 0 go 000 0g. 6O 00 0 0 e C9 0 00 00 0 0 0 69 0. 000 00.

TABLE I Pressure Polymer Amine Amine Aver age in Vacuum Product Data Amine Rate Pressure Extru der Barrel Vent VICAT Example Rate Feed 0/min. Tyae_ a/mm. atm RPM 'lm. 0 C. atm OC. No.

G 27 Ammonia 7 29.9 150 0.16 1 310 -1 3-1 7 35.4 150 0.16 3.19 152 2 3,10 2 26 7 50.4 '150 0.16 5.59 -190 3 310 A 23 49.7 -150 0.23 3.26 -157 4 3 4 32 61.2 150 0.26 6.57 188 310 6 B 31 6 23.8 '150 0. 16 0.74 '130 psia Me thyl1 8 360 300 260 0.110 -1.22 tv 8 370 300 260 0.16 2.86 it 8 370 300 260 0.16 5.06 '175 360 280 0. 16 3.55 126 13 450 315 280 0.16 5.32 142 450 3,15 280 0.16 6.81 '154 34 650 310 280 0.16 7.20 161 -12 700 315 280 0.16 8.00 -182 17 670 312 280 0.16 8.20 -183

S *0 0 0 00 0 0 w 4. 05 0 0 .0 I 000.0 e~ 0 0 *00* 0 0 00 0 000 S So.

TABLE (continued)

Pressure Polymer Amine Amine Average Vacuum Rate- Amine Rate Pressure Extruder Barrel Vent Product Data Example atm. %N VICAT No. Feed a0/min. Tvne gf'Imin. Oslo RPM TemD.0 C.

740 315 300 0.13 5.01 '164 Ammonia 850 3-15 310 0.20 7.54 1.99 775 365 310 0.23 7.63 200 775 450 310 0.1.3 4.44 160 725 450 310 0.13 2.18 1.41 825 455 310 0.110 5.58 -171 atm

53.8 350 210 0. 110 3.2 -155 Ammonia Methyl 34.0 250 31.0 0.110 7.1 160

Cy clohexy 1 20.4 275 31.0 0. 10 6.8 1.65 Ammonia 55.-1 200 310 0.110 3.3 160 34. 7 200 310 0. 110 7.0 '158 Me thyl.

0 0g 00 00 S S 6 00

0 0 a. 00 II 000 Se 0 000 0 00. e.g 0 0g 0 6mg 0

TABLE 1 (continued)

Pres sure Amine Amine Average Vacuum Polymer Amine Rate Pres sure Extru der Barrel Vent Product Data Example R ate Feed o/min. TvToe g/min. 'Osia RPM Temp. 0 C. atm. /N VICAT

7 740 315 300 0.-13 5.01 '164 16 Ammoni a 7 850 3,15 3-10 0.20 7.54 199 17 I, 775 365 3'10 0.23 7.63 200 18 It 775 450 310 0.113 4.44 160 119 It 3 725 450 310 0.13 2. 18 141 I, 6 825 455 310 0.10 5.58 '171 21 atm

Ammoni a 350 310 3.2 155 53.8 0.10 34.0 250 3'10 7. 1 '160 Me thyl1 0. Cyclohexyl 20.4 275 310 6.8 1.65 0. Ammonia 55.1 200 310 3.3 '160 34. 7 200 3-10 0. 10 7.0 158 Methyl

6 00. OS o SO 6. 0 0 50 5 0 @0 0 I S. 60 @0 60 0O 0 0 00

I 0 S S 6 5 0 6 *S 555 0 0 5 0. 0 S 0 0 0 0 0 0 0 S S 0 0 0 0 00 SO *000 000 *0 500 500 6 0

TABLE I (continued)

Polymer Ami-ne Aver age Example Rate Rate Extruder Barrel No. Feed a/mn.- Amine c/min. RPM Temn. 'C. 27 50 Ammonia 5 250 300 28 25 Methyl 2 250 29 K 100 Ammonia 400 310 L 35 Methyl 5 200 275 31 M 60 Ammonia 200 290 32 N 40 Methyl 3 -175 3'10 33 0 80 Ammonia 7 350 250 34 P 30 Methyl 2 250 3-10 Q 50 Ammonia 5 275 275 36 R Do decy 1 30 300 250 37 S 60 Aniline 3 10 310 38 T 30 7 200 260 39 U 40 Cy clohexy 1 1.5 275 275 V Isopropy 1 30 400 290 41 w 50 ki-buty 1 15 300 265 42 S 35 Ethyl 7 250 310 43 S 25 Triabloro aniline 310 44 x 50 Ammonia -12 275 310 R 50 A blend of 5% 25 300 300 ammonia., butyl amine

00 0 0 S 0 0 S 0S Se 0 000

0 0 0 01

0 0 ee 0 0 G%0 go* o* 0000 0:

TABLE I (continued)

Polymer Amine Aver age Example Rate R ate Extru der Barrel No. Feed c/min. Amine a/min. RPM Temn. 'C. 27 50 Ammonia 5 250 300 28 Methyl 2 150 250 29 K Ammonia 400 3 L 35 Methyl 5 200 275 31 M 60 Ammonia 10 200 290 32 N 40 Methyl 3 '175 3'10 33 0 80 Ammonia 7 350 250 34 P 30 Methyl 2 250 3,10 Q 50 Ammonia 5 275 275 36 R LDodecyl 30 300 250 37 s 60 Aniline 310 3-10 38 T 30 N.--joil 7 200 260 39 TJ 40 Cvclohexyl .15 275 275 V Isopropyl 30 400 290 41 w 50 n-butyl i5 300 265 42 S 35 Ethyl 7 250 310 43 S 25 Trich loro an-iline -15 310 44 X 50 Ammonia 12 275 310 R 50 A blend of 5'%0 25 300 300 ammonia, butyl1amine

EXAMPLE 46

In an extruder reactor as used in Examples 1 to

except with a configuration:polymer feed/high pressure vent/

amine feed/atmospheric vent/vacuum vent/exit die, base poly-

mer A is imidized under the same conditions as Example 7

resulting in a nitrogen content of 1.5, and bonds in its IR

spectra indicating the formation of imide groups.

EXAMPLE 47

2724 Kg/hr of a copolymer of 70/30 MMA/EA with a

[I DMF 2.7 are fed to the feed throat of a twin screw

counter-rotating tangential extruder with a screw diameter

of 51.4 c.m. The polymer is conveyed down the barrel,

fluxed, and then passed through a restrictive section which

S acts as a pressure seal. In a section of extruder barrel, *a. *o Z 15 barrel diameters long, which is isolated with regard to c* gas transfer from the rest of the extruder, ammonia is S.

06 added at the rate of 272.4 kg/hr. The ammonia is added to

the down stream port of the reaction zone and the unreacted

ammonia and reaction products exits the reaction zone on the

up stream end of the reaction zone. The vapor stream is thus a S

counter-current to the polymer stream. The pressure in the 0

reaction zone is kept at 33.42 atmospheres.

The polymer passes from the reaction zone to a vent 0 zone, at atmospheric pressure; at this zone most of the re-

c.25 0 maining methanol arid ammonia are remo- ed. The polymer is then 6 0j conveyed into a vent zone operated under reduced pressure to

aid in the removal of the last traces of ammonia and methanol.

Tie polymer then leaves the extruder through a die containing

I many holes. The many strands thus formed are cut to give

2084 kg/hr. of the final product. The product has a nitro-

gen content of 9.0% and L Vicat softening point of 200 0 C.

It is insoluble in boiling water and not attacked by mild

acids or bases. The molecular weight of the product is

within 10% of that of the starting polymer.

EXAMPLE 48

To an extruder, as described in Example 47, a co-

polymer of 96% methyl methacrylate with 4% ethyl acrylate

with DM of 0.84 is introduced at 1430 kg/hr. This

pol,ymer is compacted, melted, and formed into a continuous

stream of molten plastic which is propelled along in the

extruder barrel. Through the use of non-flighted and

reverse-flighted screw sections the extruder is divided into

zones through which the polymer can flow but vapors cannot

pass; pressure differentials of over 68 atm. can be estab-

lished between zones without vapor transport between them.

To the "reaction" zone of this extruder is added 738 kg/hr.

of anhydrous-monomethyl amine; this material is a gas under

the coi.Jition of the extrusion operation. The monomethyl

amine gas and the polymer melt are caused to come into

intimate contact by having several intensive mixing screw sections in the reaction zone. Some of the amine dissolves

in the polymer melt. The dissolved amine then reacts with

the ester units in the polymer to displace methanol and to

form six membered cyclic imide rings attached to the polymer

backbone. The excess amine and the methanol reaction product

i

'i I 1 I

r 24

in the vapor phase are removed from the extruder at a vent

located at the end of the reaction zone. A pressure regul-

ation valve at this vent establishes a pressure of 44 atm.

within the reaction zone. The polymer melt, which contains

dissolved monomethyl amine and methanol, is propelled into a

vent zone operated at atmospheric pressure. In this zone

most of the dissolved amine and methanol is removed. The

polymer next passes into a vent zone under a pressure of 0.06

atm. In the zone the remainder of the dissolved amine and

alcohol are removed. The polymer melt, now free of volatile

materials is forced through a die to form many strands of

polymer which extrude from the machine. These strands are

continuously cooled and cut to give 1195 kg/hr. of thp prod- S* uct polymer in molding powder form. The extruder is heated

S 15 to keep the barrel temperature in all zones at 280 0 except

the initial feed zone which is kept at 150 0 C. The materials 000 collected from the three vents are processed in such a way

to recover most of the monomethylamine in a pure form for

recycle to the reaction zone, and a solution of methanol with

some monomethyl amine in it. There are several commercial

uses for such a solution, such as in the production of mono- ethyl amine by the reaction of ammonia with methanol.

The polymer produced by this process has a DMF

0.76. The reduction in molecular weight upon imidization is

25 due to the loss of weight due to the chemical transformation

I of the side chains and not to any significant reduction in the length of the polymer backbone. the length of the polymer backbone.

This polymer has a Vicat softening point of 182 0 C.

measured in accordance with ASTM D1 525-70. It is clear and

colorless and can be processed by all the normal techniques

used to prepare useful articles .fr9, thermoplastic materials.

The polymer has a Charpy unnotched Impact Strength of 7.5 ft.-

Ibs. measured in accordance with ASTM D-256-56.

EXAMPLE 49

g/min. of pMMA is added to a Werner Pfleiderer

twin screw intermeshing extruder type ZDS-L 28. To an in-

jection port near the feed end of this extruder 10 g/min. of

methylamine is added at 170 atm. The unreacted methylamine

and volatile products are removed from the extruder at a

io vacuum vent near the die end of the extruder. The resulting

polymer has a nitrogen content of 8.4% and gives an IR

15 spectra which shows that the polymer is essentially all imide. e*

EXAMPLE

50 g/min. of pMMA is added to a 1" Killion single

Sscrew extruder. To this extruder ammonia is added at 8 g/min.

at an inlet port near the feed end of the extruder. The

20 unreacted ammonia and reaction products are removed at a vacuum vent near the front end of the machine. The resulting cj

product is a clear colorless polymer soluble in DMF.

:EXAMPLE 51 (Comparative)

A. Attempted repeat of Example 7 of West German

Patent DAS 1,077,872.

As in the reference, an aqueous ammonia (NH 3 /H 2 0

ratio of 80/20 by wt.) solution was introduced through a vent plug of a single screw at a rate of 5 cc/min. to a 40 g/min.

feed of pMMA (7 SP/C of The extruder was a 1" Killion

with an 1/d of 24/1 and a 1/2" x 2" vent port located 60% of

the way from the feed to the die, the vent being equipped

with a plug with an inlet port which was, in turn, connected

by a steel line to a LAPP LS-5 pump which, in turn, was

connected to a feed cylinder. The extruder was run at 100

RPM with a barrel temperature of 265 0 C.

With a first screw having a channel width reduction

from 0.255 to 0.110 (going from vent area to die), the highest

ammonia pressure obtainable was 15 atm. since the pressure

seemed to be venting through the die. Attempting to achieve

the pressure specified in the reference: the polymer feed

rate was increased to 70 g/min., but the ammonia pressure

15 remained at 15 atm.; the ammonia rate was increased to S" *0 11 cc/min. with resultant ammonia pressure increase to S** atm., but the pressure still seemed to be venting through the

die.

Attempting to achieve the pressure conditions

reported in the reference, a second screw, having a channel 0 0 width reduction of 0.200 to 0.050, a screen pack, and an S 0 ammonia rate of 5 cc/min. were used, but again only 15 atm.

ammonia pressure could be obtained since the pressure seemed

to vent through the polymer feed port. However, the die

2 pressure was 50 atm. leading one to believe that this is 1 11

where pressure was measured in the reference. The pMMA had

to be force fed to keep the system running. The ammonia rate

I i

S- !27

was increased to 10 cc/min. but the pressure did not increase.

No imidization was observed in any of these attempts

to repeat Example 7 of the reference.

EXAMPLE 52 (Comparative)

A. In accordance with the invention, an 0.8"

Welding Engineer's twin screw extruder having the configur-

ation described in Examples 1-6 is used to completely imidize

a pMMA having a [L DMF of 1.65 with non-aqueous ammonia under

a pressure of 53 atm. and temperature of 260-270 0 C. at a

point about 1/3 the way down the screw. A vacuum of 0.9 to C/qmosphe res 0.001/is applied to the vacuum vent.

A smooth continuous product strand exits the ex-

truder. The product does not require drying, and it can be

further processed without intermediate steps. No ammonia :15 vents into the environment, and all by-products are replace- 6 able.

The product is poly(glutarimide), and is tested for thermal stability by the dynamic thermogravimetric analysis

method (TGA) with results reported in Table I.

B. To show the critical importance of the amine

being non-aqueous and the subatmospheric pressure being

applied to at least one vent port, a comparative experiment

•was conducted using the same conditions of A, supra, but using

S* aqueous ammonia (NH3/H2 0 ratio 80/20 by wt.) and plugging :he

vacuum vent. The product exited the extruder in foamed,

discontinuous masses propelled by the ammonia pressure at

high velocity and was stopped by a shield mounted about 4 feet from the extruder die. Large quantities of ammonia vented from the die into the environment. The product was ground to a fine powder and had to be dried. It was vacuum dried at 120 0 C. for 16 hours and tested for thermal stability by dynamic TGA. with the results reported in Table .I,

Although the products produced in accordance with

the invention supra) and in this comparative experiment, B, both had equal degrees of imidization (100%) and melt

viscosity, the comparative experiment produced a product which

was significantly less thermally stable than the analogous

product of the invention. The results in Table II imply that

at typical processing temperatures, around 300 0 product A

only loses around 1% of its weight, whereas product B loses

over This difference can mean the difference between a 4. 15 .5 no bubble, smooth surfaced product and a bubble-containing, 00*0 rough-surfaced product.

TABLE II THERMAL STABILITY

DYNAMIC TGA, TEMP. INCREASE RATE 20 0 C./min.

S 5 Weight Temp., oC., Air or Nitrogen, at which total Loss wt. loss is as indicated

AIR NITROGEN S S A B A B 00 W 1 285 100 300 105 0*000* 2 370 175 400 275

3 385 350 440 385

4 395 380 420 405

400 390 420 410

i

NOTE: A represents invention

B is comparative.

EXAMPLE 53

This Example compares the polymers prepared in

Graves U.S. Patent 2,146,209, Schrbder et al U.S. Fitent

3,284,425 with the polymers of the invention.

A. GRAVES

The polymer prepared in Examples I and II of the

Graves Patent are supposedly polymethacrylimides. However,

according to these Examples the polymers actually produced

were soluble in dilute ammonia and boiling methanol. The

polyglutarimide polymers of the present invention are insol- 9 uble in dilute ammonia and insoluble in boiling methanol. *9 The Graves product appears to be a copolymer of methacryl- S

"15 imide, methacrylamide, and ammonium methacrylate.

B. SCHRODER ET AL AUTOCLAVE

For purposes of comparison, Example 1 of U.S.

3,284,425 is repeated using 120 parts polymethyl methacrylate

heated for 7 hours at 230 0 C. in a Parr stirred autoclave with 20 129 parts of a 33 1/3% aqueous solution of methylamine and

780 parts water. A pressure of 31 atm. develops. The re- action product comprises a watery phase and 32.7 parts of a

99999 solid polymer which was washed and analyzed to have a nitro-

gen content of 8.5 The 32.7 parts represents 34.6%

625 of the initial charge.

The Schroder polymer is compared to the polymethyl-

methacrylate/methyl amine reaction product prepared in the

extruder in accordance with the invention with the results

reported in Table III.

These data show that the Schroder et al polymer is

clearly less thermally stable than the polymer prepared in

accordance with the invention; the Schroder et al polymer

exhibits weak, ill-defined glass transition temperature as

compared to the polymer of the invention; and it begins to

soften at a lower temperature (DTUFL and Vicat). The trans-

lucency of the Schroder et al material seems to indicaLe a

non-uniform imide level, as compared to the transparent, and

hence uniform, polymer of the invention. The difference in

water resistance indicates inferior properties of the Schr8der

*15 et al polymer.

EXAMPLE 54

Six and one-half parts of the poly(glutarimide) poly- mer produced in accordance with Example 18 are blended with

three and one-half parts of the MBS impact modifier produced Spec Ifrc-lon 3S704 in accordance with Example 1 of U.S. Patent/Applieation S.N. 3,5440e of June 19, 19 and 0.5 weight percent antioxidant

at 460-510°F. in a vacuum-vented single screw extruder to produce translucent strands which are then pelletized, dried .at 90 0 C. and injection molded at extrusion temperatures. The

**:925 polymer blend produced had a Vicat of 185 0 a DTUFL (oC.)

of 180 (66 psi), 160 (264 psi), and 170 (264 psi annealed). The product had a notched Izod impact strength of 1.1 ft.-lbs.

/in. and tensile modulus of 4 x 10 tensile strength of 9 x

3 psi at break. psi at break.

EXAMPLE

Compositions similar to that of Example 4 except

using the impact nodifier produced in accordance with Example

1 of U.S. Patent 3,808,180 with imide to modifier ratios of

3/2 and 1/1 gave similar results. Sibstitution of MBS and

ABS modifiers gave excellent balance of properties.

EXAMPLE 56

A composition as per Example 54, except with the

ratio of poly(glutarimide) to MBS modifier of 6 parts to 4

parts, gave translucent articles having the following prop-

erties, Vicat 135°C.; DTUFL 1200C. (66 psi), 100 0 C. (264 psi);

notched Izod 2.5 ft.-lbs./in.; tensile modulus 3 x 10 psi;

tensile break strength 6 x 103 psi. 1

EXAMPLE 57 S s* Example 54 was repeated except substituting one

part of polycarbonate for one part polyglutarimide, producing

opaque polymer blends having the following properties, Vicat

170 0 DTUFL 170 0 C. (66 psi), 135 0 C. (264 psi), 145 0 C. (264 K. 20 psi, annealed); notched Izod 2.1 ft. lbs./in.; tensile modulus

3 x 105 psi; tensile break strength 7 x 10 3 psi. S S. EXAMPLE 58

Example 54 was repeated except using 5.9 parts poly-

glutarimide to 4.1 parts impact modifier, and substituting for 0 the MBS impact modifier one of the following formula: Bd/St//

MMA//St//MMA/AN/St: 71/3//3//11//4/4/4.

gidkh

K -32-

The properties of the resultant blend were as

follows: Vicat 1.60 0 DTUPL 1.470 C. (66 psi), IAO0 C. (264 psi); notched Izod 1.5 ft.-lbs./in.; tensile modulus 3 x

3 tensile strength at break 8 x 10 psi.

**4~*OO

*0 0 CS 00 6

0S 00 0 C 0@ 0. C* S S S.

0

6* CO S 0*90 00 S e.g '9

6

C

S 9B00*0

C

S. C 0

Ir LC

rI-L- f @0 0, 0 B *0 *i B 06 i B. *6 0 *0 d 0 0 S0 0 0 0 s Z 0 S2 0 6 0 6 0 S 0 l 0 0 0 0 0Se 0 9 0 6 0 0 0* S 00 00 *OS Se SO 5000 055

'i

TABLE III AUTOCLAVE EXTRUDER TEST (SCHRODER) (INVENTION)

Nitrogen, 0.2 8.5: 8.3 Intrinsic Viscosity Melt Rate Flow Condition C 0.45 rl In DMF insoluble 0.35 In 95/5 DMF/Formic Acid 0.24 0.20 ri' In tetrahydrofuran insoluble soluble 177 I Vicat Temperature oC. DTUFL by TMA OC. 170 90 122

IE: Tensile Impact (avg. of 5 measurements with large amount of scatter and therefore low confidence value) Tensile 20.7 13.4

Break 'strength, psi 12,800 12,100 Modulus, psi 519,000 518,000 After 35 hrs. in boiling water weight increase 5.2 3.3 Surface condition badly attacked good optical properties opaque/white clear/light yellow Original Optical Properties translucent/grey clear/yellow Differential Thermal Analysis (DTA) Nature of Transition weak ill defined sharp well defined Transition Temperature, OC. 194 179 Thermogravimetric Analysis (TGA) 1% Wt. Loss (Air) oC. 240 365 1% Wt. Loss (N2) oC. 245 395 3% Wt. Loss (Air) oC. 360 395 3% Wt. Loss (N2 OC. 395 410 Nuclear Magnetic Resonance Analysis, presence of signal at 3.14C indicating presence of at least 1% by weight amide present absent groups.

I g 0 e.g 0. gO 0* CS 0 gO gg 00 gg OS S 0 S 0 S 0 0 0 00 5 0 S S 0 0 0S 0 0 6 0 0 0 S 0 0 00 *0 S 0 e.g SO egO 000 0 0

TABLE III AUTOCLAVE EXTRUDER TEST (SCHRDER) (INVENTION)

Nitrogen, 0.2 8.3 Intrinsic Viscosity Melt Rate Flow Condition C 0.45 In DMF insoluble 0.35 In 95/5 DMF/Formic Acid 0.24 0.20 In tetrahydrofuran insoluble soluble Vicat Temperature °C. 170 177 DTUFL by TMA °C. 90 122 Tensile Impact (avg. of 5 measurements with large amount of scatter and therefore low confidence value) 20.7 13.4 Tensile Break strength, psi 12,800 12,100 Modulus, psi 519,000 518,000 After 35 hrs. in boiling water weight increase 5.2 3.3 Surface condition badly attacked good optical properties opaque/white clear/light yellow Original Optical Properties translucent/grey clear/yellow Differential Thermal Analysis (DTA) Nature of Transition weak ill defined sharp well defined Transition Temperature, °C. 194 179 Thermogravimetric Analysis (TGA) 1%*Wt. Loss (Air) oC. 240 365 1% Wt. Loss (N2) oC. 245 395 3% Wt. Loss (Air) oC. 360 395 3% Wt. Loss (N 2 oC. 395 410 Nuclear Magnetic Resonance Analysis, presence of signal at 3.14 indicating presence of at least 1% by weight amide present absent groups.

THE CLAIMS DEFINING THE I NVEBNTION ARE AS FOLLOWS

1. A process for the imidization of an imidizable polymer which

comprises reacting said polymer witn ammonia or a primary

amine in an extruder under substantially anhydrous conditions,

I as hereinbefore defined, at a temperature of from 200 to

S4500 C. while applying subatmospheric pressure to at least one

vent port of the extruder.

.r 2. A process as claimed in Claim 1 wherein the polymer I' is derived from at least one acrylic and/or methacrylic acid

'ester.

S3. A process as claimed in Claim 1 or 2 wherein the Sammonia or primary amine is introduced through an extruder addition port at a pressure of from 1 to 1000 atmospheres.

4. A process as claimed in any of Claims 1 to 3 6

wherein the average residence time is 0.1 to 1000 seconds.

A5 process as claimed in S any of Claims 1 to 4 Swherein the degree of imidization is determined by control of the average residence time and temperature.

6. A process as claimed in any of Claims 1 to wherein the temperature is from 300 to 375°C.

7. A process as claimed in any of Claims I to 6

further characterized as being carried out in the absence of A solvent.

8. A process as claimed in any of Claims 1 to 7

further characterized as carried out in the absence of a

catalyst.

9. A process as claimed in Claim 1-wherein anhydrous

ammonia is introduced through an extruder addition port at

a pressure of from 1 to 500 atmospheres, the average resid-

ence time is maintained at 30 to 300 seconds, a partial

pressure of Ov9 to 0.01 atmospheres is applied to at least one

vent port, the temperature is maintained at from 325 to 0 375 0 and the reaction is conducted in the absence of sol-

vent.

0 0

S. 10. A process as claimed.in any of Claims 1 to 8

wherein a partial pressure of from 0.9 to 0.01 atmospheres

is applied to the vent port.

11. Polymer whenever produced by a process as claimed

in Claim 1.

12. Polymer whenever produced by a process as claimed

in any of Claims 2 to

13. A composition comprising a thermoplastic polymer

containinq imide units of the structural formula

0 N 0 C C

S-CH 2 CH2

Claims (1)

1. wherein RI, R2 and R 3 represent hydrogen or C1 to C 2 0

   unsubstituted or substituted alkyl, aryl, said polymer being

   further characterized as non-crosslinked and soluble in

   dimethyl formamide, and having a degree of thermal stability

   as measured by thermogravimetric analysis in an air

   atmosphere such that the temperature at which said polymer

   has 1% by weight decomposition is at least 285 0 C.

   14. A composition as claimed in claim 13 which comprises

   a single stage polymer containing said imide units and/or 1 C a multi-stage polymer whose outer stage contains said Ge C imide units. oe b 1 o o 15. A composition as claimed in claim 14 which comprises

   from 40 to 90% by weight of single stage polymer and from

   to 60% by weight multi-stage polymer. C

   16. A composition as claimed in any of claims 13 to C Gee C S wherein the polymer contains other units derived from one

   or more ethylenically unsaturated monomers selected from CC LO Ge 00 Ge the group consisting of acrylic and methacrylic esters,

   acrylic and methacrylic f-id, acrylonitrile, styrene, ethylene and butadieae.

   17. A composition as claimed in any of claims 13 to 16 wherein

   to 100% of the polymer units are imide.

   18. A composition as claimed in any o:.f claims 13 to 16

   wherein 1 to 35% of the polymer units are imide.

   IL A -36-

   19. A composition as claimed in a<iy of Claims 13 to 18

   wherein the polymer contains said imide units and units

   derived from at least one acrylic and/or methacrylic acid

   ester, the numerical ratio of the imide un ks to acrylic

   and/or methacrylic units being from 1:2 to 9:1.

   A composition as claimed in any of Claims 13 to 19

   wherein the thermoplastic polymer has an intrinsic viscosity

   in dimethyl formamide of from 0.1 to

   21. A composition as claimed in any of Claims 13 to

   further characterized as being soluble in tetrahydrofuran and dimethyl sulfoxide.

   22. A composition as claimed in any of Claims 13 to 21 which further includes an impact modifier.

   ,-23 A composition as claimed in Claim 22 wherein the impact modifier is a multi-stage polymer. 0

   24 A composition as claimed in Claim 22 or 23 wherein 0 the impact modifier comprises at least one of the type acryl-

   onitrile/butadiene/styrene, methyl methacrylate/butadiene/

   styrene and all acrylic.

   A composition as claimed in any of Claims 13:. to 24

   in the form of sheet, rod, tube, powder, granule or molded

   article.

   26 A composition as claimed in Claim 13 prepared by a

   process according to any of Claims 1 to ri 27. A composition as claimed in any of claims 14 to 2 prepared by a process according to any of claims 1 to

   DATED this 16 day o f Novemnbe r 1979.

   DAVIES COLLISON

   Patent Attorneys for

   ROHM AND HAAS COMPANY

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