JPH04246450A - Polymer composition capable of masking odor - Google Patents

Abstract

PURPOSE: To mask an unpleasant smell discharged during production or processing at high temp. and to prevent fading or discoloration by compounding a specific phenylethyl cyclohexyl ether with a plastic.

CONSTITUTION: Phenylethyl cyclohexyl ether represented by the formula (wherein R₁, R₂, R₃ and R₄ are methyl or H) (B) is compounded with plastic (A) such as poly(N-lower alkyl)dimethylglutarimide or (meth)acrylic copolymer to produce a polymer compsn. masking an offensive smell. The B-component can be produced by reacting a phenetyl alcohol deriv. with cyclohexene and the proper compounding amt. thereof is about 0.01-1 wt.% of a polymer. Further, an oxidation inhibitor, a lubricant (e.g.; stearyl alcohol), an ultraviolet stabilizer (e.g.; benzophenone) and an impact resistance improving agent can be compounded.

COPYRIGHT: (C)1992,JPO

Description

[Detailed description of the invention]

The present invention relates to the use of phenylethylcyclohexyl ether to mask undesirable odors released during high temperature manufacturing or processing of certain polymers and to odor reduction methods containing this odorant. The present invention relates to a polymer composition. Phenylethyl cyclohexyl ether (odorant) also does not lead to undesirable side reactions and color fading problems in polymer compositions. Phenylethyl cyclohexyl ether (an odorant) is useful in plastics such as polyglutarimide and (meth)acrylic copolymers.

Glutarimide is an amine or ammonia-based (meth)acrylic homopolymer such as methyl methacrylate/ethyl acrylate (MMA/EA), methyl methacrylate/methyl acrylate (MMA/MA).
), methyl methacrylate/methacrylic acid (MMA/M
AA), and methyl methacrylate/butyl acrylate (MMA/BA). Amines and ammonia are known to have very low odor limits (eg ppm), so that residual amines or ammonia released during imide processing can produce easily detectable undesirable odors. For example, the odor threshold (i.e., if the odor is undesirable) for the following composition is monomethylamine - 3.2 ppm
, dimethylamine - 0.34 ppm, trimethylamine - 0.00044 ppm and ammonia - 5.2 ppm
m [J. E. Amoor's R&H Industry
real SafetyDir. Conference
e, “Odors, Helpful Warnin’
g and Harmful Effects” (6
/1/87)]. Therefore, the undesirable odors of monomethylamine, dimethylamine, trimethylamine and ammonia are easily noticed by workers producing or processing polyglutarimide or by consumers. Although complete removal of residual amine or ammonia is highly desirable, it has not been possible. Alternatively, the next best approach is to mask undesirable amine and/or ammonia odors.

[0003] US Patent No. 4,246,374 (Kop
Chik) discloses thermally stable polyglutarimide polymers and practical methods for their production. These polymers, especially those made from poly(methyl methacrylate) and monomethylamine or ammonia in a devolatilizing extruder, are useful as glazing or protective materials, and have higher usage than other transparent thermoplastics. Has acceptable impact resistance and elasticity at temperature. The main markets are architecture/construction, electrical/
electronics, appliances, transportation, office equipment, lighting,
Includes medical devices, optical lenses and consumer products.

The Kopchik patented thermoplastic polymer has the following structural formula:

embedded image (wherein X1, X2 and X3 are independently hydrogen or unsubstituted or substituted C1-C20-alkyl,
aryl or aralkylarkaryl or mixtures thereof, the polymer is further non-crosslinkable, soluble in dimethylformamide, and as determined by thermogravimetric analysis (TGA). It is characterized by having such thermal stability that the temperature at which it decomposes 1% in air is 285°C or higher.

The basic reaction for producing imides is described in Graves US Pat. No. 2,146,209, German Patent No. 1,077,872 and German Pat.
, by the reaction of urea, butylamine, dodecylamine or octylamine with poly(methyl methacrylate) or poly(methacrylic acid) as disclosed in No. 369. U.S. Patent No. 3,284,425 and British Patent No. 926,629 to Schroeder et al.
No. 1, poly(methyl methacrylate) to imidized acrylic resins by reacting with ammonium hydroxide, ammonium phosphate, alkyl amines, or by partially reacting with ammonium hydroxide and then reacting with alkyl amines. The route is disclosed. British Patent No. 1,045,229 describes methacrylic acid/methacrylonitrile (MMA/MAN) copolymers or Chemical modification of terpolymers is disclosed. German patents 1 and 2
No. 47,517, No. 2,041,736 and No. 2,
No. 047,096 discloses methacrylamide/methyl methacrylate (MAN/MMA) copolymers, inert solvents, and heating to achieve imide formation with ammonia evolution. The earliest patents and documents relating to the preparation of imidized acrylic resins via the reaction of ammonia and primary amines with poly(methyl methacrylate), such as U.S. Pat. No. 3,284,425, are It relates to an autoclave batch process requiring long heating times, typically 7 hours or more, in the presence of a suspending solvent. U.S. Pat. No. 3,557,070 discloses the production of methacrylic anhydride units from an ethylene/isopropyl methacrylate copolymer by heating the copolymer to the decomposition temperature of the isopropyl ester (325°C), which then reacts with gaseous ammonia. A method of making ethylene/methacrylic acid/methacrylic acid terpolymers by providing methacrylic acid and methacrylic acid residues in the polymer chain is disclosed. This reaction is carried out neat without the use of solvent. Although U.S. Pat. No. 3,557,070 does not state that these reactions occur in an extruder, the Derwent abstract of that patent states that these reactions can occur in an extruder. It is being Using an extruder as a polymer reactor can produce copolyester
J. Applied Polymer Sciences
e12, 2403 (1968); Preparation and properties of copolyesters polymerized in vented extruders], Nylon products [Modern Plastics, Aug.
st 1969-Warner Pfleiderer
; direct extrusion of nylon products from lactams] and graft polymerization of polyolefins [Steinkamp et al., US Pat. No. 3,862,265]. West German Patent No. 1,077,872 discloses an extrusion process for the imidization of acrylic polymers using an aqueous ammonia solution, but the product is a foamed strand with insufficient thermal stability and is not useful. It requires further processing before it can be used to make products. Also,
The process is not commercially viable in that the foamed polymer exits the extruder under high pressure and with free ammonia vapor. As mentioned above, the following structural formula

embedded image (wherein X1, X2 and X3 are independently hydrogen or unsubstituted or substituted C1-C20-alkyl,
aryl or aralkylarkaryl, or mixtures thereof, the polymer is further non-crosslinkable, soluble in dimethylformamide, and T
Producing a polyglutarimide characterized by having a thermal stability such that the temperature at which the polymer decomposes 1% in air, as measured by GA, is 285°C or higher and processing it with cyclohexyl phenylethyl ether. Can be done.

(Meth)acrylic copolymers (ie, resins such as about 80% or more alkyl acrylates) have excellent weather resistance and good chemical resistance, as well as glossy, colorless clarity and significant surface hardness. It is known. These properties make them useful as materials for a wide range of applications. Acrylic monomers are supplied for conversion into coating resins, cast sheets, rods and tubes. Acrylic resins are extruded into sheets or profiles.
es) or as beads or pellets for injection molding into magnifying lenses, automobile taillights and lighting lenses. Acrylic monomers can be polymerized by a free radical method using peroxides and the like. For molding and extrusion compounds, methyl methacrylate is usually copolymerized with other acrylates, such as methyl or ethyl acrylate. There are four basic polymerization methods currently in use: bulk polymerization, suspension polymerization, emulsion polymerization, and solution polymerization.

Phenylethylcyclohexyl ether can be used to mask undesirable odors released during high temperature manufacturing or processing of polymers other than polyglutarimide. For example, during the production and processing of (meth)acrylic copolymers, insufficient or no outgassing can result in undesirable odors that are unpleasant or bothersome. This is quite common in unvented single or twin screw extruders and injection molding machines. This odor may originate from residual monomers and/or mercaptans used in the manufacture of plastics to control molecular weight. For example, during the processing of (meth)acrylic copolymers, methyl methacrylate monomer has an odor limit of 50 to 340 ppb, and n-alkyl mercaptan has an odor limit of 0.5 ppb.
It has an odor limit value of 5 to 200 ppb [J. E. A
moor, Ph. D. R&H Indus
Trial Safety Dir. Confere
nce, 6/1/87 “Odors, Helpf
ul Warning and Harmful Ef
[see ``Fects'']. Phenylethyl cyclohexyl ether (PECE) masks residual monomer and/or mercaptan odors associated with (meth)acrylic copolymer production or processing.

The weather resistance and optical properties of acrylic resins are superior to many other currently available plastics. They also have good electrical and chemical properties. Acrylic resins will not yellow or stress crack, and will withstand long-term exposure to weather and direct sunlight. In extreme cases, such as exposure to mercury lamps, it is recommended to add ultraviolet absorbers (UVA). The following structural formula

[Formula 7] (wherein, Z1 is H, CH3, CH3CH2, CH3CH
2CH2, CH3CH2CH2CH2 or

The meth(acrylic) copolymer of cyclohexyl phenethyl Can be produced and processed with ether.

Phenylethylcyclohexyl ether is used in perfumery and is known to be a pheromone, so it can be used in insecticides. For example, U.S. Pat. No. 4,374,74 to Kiwala et al.
No. 6 also contains Lasioderma S for enhancing the fragrance of fragrances, scented products and colognes.
Cyclohexylphenylethyl ether and its derivatives are disclosed for combating tobacco leaf beetles of the species E. erricorne (F). Pheromones with a pleasant scent are also useful in controlling insects, but at the same time do not cause aversion to the individual or group applying the pheromones to the area inhabited by the insects to be controlled.

In particular, Kiwala et al.

embedded image (wherein R1, R2, R3 and R4 are the same or different and are methyl or hydrogen. However, if one of R2, R3 and R4 is methyl, R2, R3 and R
The other two of 4 are hydrogen), or the preparation of the compound by reacting a phenethyl alcohol derivative with cyclohexene.

Modern Plastics Enc
Vince in yclopedia (1989)
nt A. The Lindgren article discloses fragrance concentrates that can be dispersed in a thermoplastic resin matrix. Fragrances are sold as dry pelleted additive systems and serve as a clean and safe way to incorporate functional or decorative fragrances into a wide range of plastic processes. Fragrances are available in single fruits and florals, and are synthetically refined fragrances (complex fragrances).
(ine fragrances) or functionally deodorizing types, these concentrates are resin-based and are compatible with most olefinic, cellulosic, and poly(vinyl chloride) (PVC) compounds. Manufactured. These can be blown or cast into films, injection molded, blow molded, foamed or extruded.

The object of the present invention is to produce plastic compositions that mask undesirable odors and are free of undesirable color formation. Furthermore, it is an object of the present invention to produce imide compositions that mask undesirable amine and ammonia odors. Additionally, it is also an object of the present invention to produce polyglutarimide compositions that mask unpleasant amine and ammonia odors and are free of undesirable color formation. It is also an object of the present invention to teach a method for producing plastic compositions that masks undesirable odors and does not involve the formation of undesirable colors.

The following structural formula

A polymer composition has been found comprising phenylethyl cyclohexyl ether having the formula: wherein R1, R2, R3 and R4 are the same or different substituents selected from methyl or hydrogen. This resulted in a polymer composition that was able to simultaneously mask the plastic odor present during high temperature processing without the undesirable consequences of side reactions and fading.

It has been found that the addition of phenylethyl cyclohexyl ether (PECE) to the polymer composition significantly improves odor masking. For example, the addition of PECE to glutarimide masks undesirable amines and/or ammonia to the human sense of smell. Additionally, PECE was found to be the most preferred masking agent or fragrance in terms of color production (based on yellowness index values) when added to polymer compositions (
(See Example 1).

The concentration of phenylethylcyclohexyl ether that is effective is about 0.01 to 1.0% by weight, based on the plastic (eg, polyglutarimide or (meth)acrylic copolymer) in the polymer composition. At low concentrations the odorant is not very effective, and at high concentrations the odorant is fully effective but not at an efficient or economical rate. From about 0.01 to about 0.10% by weight of odorant is preferred. An effective amount of phenylethyl cyclohexyl ether is such as would be added by one of skill in the art and would act to impart the desired odorant characteristics to the polymeric composition.

The plastics of this invention are useful in applications that do not require high clarity or visible light transmission, such as sheets, films, molded articles or extruded products. Such useful products, where stability to light and heat is desired, include windows, protective shields, housings, etc. for heat-emitting light sources, especially those that emit ultraviolet radiation or are severely exposed to it during use. It is. For something like this,
Lighting for cars, trucks, airplanes, buses, etc., especially headlights or taillight enclosures, high intensity discharge lighting such as metal vapors, mercury sources, sodium vapors, sunroofs for cars, buses, trucks, boats, etc.

Plastics applicable to the present invention include, but are not limited to, polyglutarimide and (meth)acrylic resins. Glutarimide polymers are preferably prepared by the method of U.S. Pat. No. 3,246,374, but also by other methods, such as the reaction of poly(methyl methacrylate) with monomethylamine in a pressurized kettle at elevated temperatures. , a polymer with a high proportion of methyl methacrylate units and a primary alkylamine,
using reaction in a suitable solvent, reaction of polymers with a high proportion of N-methyl methacrylamide units to eliminate methylamine, or reaction of polymers with a high proportion of glutaric anhydride units with ammonia or methylamine. You may. Such polymers may not exhibit the thermal stability or transparency of the polymers made by the method of US Pat. No. 3,246,374. Here, the thermal stability is expressed by a weight loss of not more than 1% at a temperature of 285° C., as determined by thermogravimetric analysis, and by the solubility in solvents such as dimethylformamide and tetrahydrofuran.

The acid content of polymers made by the process of US Pat. No. 3,246,374 will normally exceed about 0.5% by weight, but never exceed 6%. Glutarimide polymers made by other processes will exhibit similar acid content, but polymers made by solution processes are considered to be on the lower end of this range. Typical acid contents of the matrix polymers of the present invention range from about 2 to
A value of about 3.5% by weight (calculated from about 0.10 to about 0.60 milliequivalents/gram. The analytical method is based on U.S. Pat. No. 4,72
No. 7,117).

Odorants may be used in combination with plastics, especially glutarimide polymers containing low or no acid content, such as those taught in US Pat. No. 4,727,117. . Odorants can be added to plastics and glutarimide polymers by secondary compounding of additives and destabilizing powders or pellets of plastics and glutarimide polymers, or by addition during or before the imidization or acid reduction steps. . In order to mask the odor, it is preferred that the odorant be added at the end of the glutarimide production. Odorants and other additives may be added before, during or after polymer production and during imide formation.

Another method is to add other additives such as toners, lubricants, etc. to the molten glutarimide or imide to become acid-reduced glutarimide polymers prior to extrusion into pellets, strands, sheets or films.
The phenylethyl cyclohexyl ether is added to the polymer composition along with antioxidants, colorants, UV stabilizers, hindered amine light stabilizers, impact modifiers, pigments, fillers, fibers, flame retardants, etc. This method exposes the polymer and additives to less thermal history than reprocessing an already extruded polymer. An effective amount of an additive is an amount that one of ordinary skill in the art would add and which acts to impart the additive's desired characteristics to the polymer composition. Polymer compositions containing effective amounts of additives include (meth)acrylic resins, poly(vinyl chloride), poly(amide),
Polycarbonate, polyester, SAN (styrene/
acrylonitrile), ABS (acrylonitrile/butadiene/styrene), MBS (methyl methacrylate/
butadiene/styrene) polymer or 2-stage or 3-stage
The core-shell of the corrugation can be mixed with an all-acrylic impact modifier.

Very low amounts of toner, colorants (such as pigments and dyes) and colorants or concentrates can be used to correct undesirable colors found in the polymer. Color Index Number (USA, So
Society of Dyers and Colouri
sts) may be selected for use in the polymeric compositions described herein: Pigment Black 7, Pigment White 6, Pigment White 21, Pigment White. Green 7, Pigment Blue 15, Solvent Orange 60, Solvent Red 179, Solvent Green 2
8, Solvent Blue 45, Solvent Blue 101,
Solvent Violet 14 and Disperse Yellow 54. An example of a useful toner is Irisol NTM (1
-p-toluidino, 4-hydroxyanthraquinone). Additionally, the use of blue colorants is preferred to correct yellowness problems.

Lubricant is a known component of acrylic molding materials and serves to prevent sticking to hot metal surfaces and release from the mold or die lip. Such lubricants include high molecular weight alcohols such as alcohols having from 12 to 24 carbon atoms, esters, especially long chain alkyl esters of high molecular weight acids such as butyl or stearyl stearate; glycols such as ethylene glycol monostearate. Examples include monoester. Preferred is stearyl alcohol. When used, the concentration of lubricant is about 0.05 to about 0.50% by weight of the polymer, preferably about 0.30%.

For the processing and shaping of polyglutarimide, antioxidants (thermal stabilizers) can be present without impairing the UV stability of the stabilized composition. A preferred class of heat stabilizers are organic phosphites such as Tris(
aryl)- or tris(alkylaryl)- or tris(alkyl)-phosphite. Another preferred class are organic phosphonites such as trisaryl, trisalkaryl- or aryldiallyl phosphonites such as aryl-di(alkylphenyl)phosphonites. Acid stable tris(2-alkylaryl) phosphites such as tris(2-t-alkylaryl)
Phosphites or aryldi(2-alkylaryl)phosphonites are preferred. Particularly preferred heat stabilizers are tris(nonylphenyl) phosphite [TNPP], tris(2,4-di-t-butylphenyl) phosphite [IngafosTM 168], and distearyl pentaerythritol diphosphite [Weston 618].
TM] and tetrakis(2,4-t-butylphenyl)4,4'-biphenylene diphosphonite [PEPQ]
It is. Another preferred class of antioxidants are thioesters such as dilaurylthiodipropionate, ditridecylthiopropionate and distearylthiodipropionate.

[0024] The odor masked polymer may also contain UV stabilizers. UV stabilizers are known additives for thermoplastics such as the glutarimides of the present invention and include hydroxybenzophenones, salicylate esters and benzotriazoles. Benzotriazole stabilizers are preferred. The amount of UV stabilizer required is from about 0.10 to about 0.50% by weight of the polymer composition. Hindered amines are useful for ultraviolet light stability (UV light stabilizers). Preference is given to hindered amines in which R1=R2=R3=R4=methyl and X=H. Examples of hindered amines that can be employed include bis-(2,2,6,6-tetramethyl-4-piperidinyl)sebacate;
-piperidinyl)benzoate, 1,2,3,4-tetrakis(2,2,6,6-tetramethyl-4-piperidinyl)butanetetracarboxylate; 1,2-bis(
2-oxo-3,3,5,5-tetramethyl-1-piperidinyl)ethane; 1-(3,5-di-t-butyl-4
-hydroxyphenyl)-2,2-bis(2,2,6,
6-tetramethyl-4-piperidinyloxycarbonyl)-hexane; poly(1-oxyethylene(2,2,6
,6-tetramethyl-1,4-piperidinyl)oxysuccinyl; N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine; (4-hydroxy- 2,2,6,6-tetramethyl-
1-piperidine) ethanyl; poly(2-(1,1,3,
3-tetraethylbutylimino)-4,6-triazinediyl-(2,2,6,6-tetramethyl-4-piperidinyliminohexamethylene-(2,2,6,6-tetramethyl-4-pipe lysinyliminohexamethylene-(
2,2,6,6-tetramethyl-4-piperidinyl)imino) or its N-methyl derivative. For reasons of non-volatility and compatibility, the following structural formula

embedded image (wherein R1, R2, R3 and R4 are methyl,
and X is H, methylene or -CH2-CH2-O-
Particularly preferred are hindered amines containing one or more groups with ). These groups may be bonded by aliphatic esters, aromatic esters, heterocyclic carbon-nitrogen compounds such as melamine groups, and the like. Particularly preferred is bis(2)
, 2,6,6-tetramethyl-4-piperidyl) sebacate. An example of a benzotriazole stabilizer useful for the protection of glutarimide and other polymers by acting as an absorber in the harmful portion of the UV spectrum is 2-(2'-hydroxy-5'-methylphenyl)
Benzotriazole; 2-(2'-hydroxy-3',
5'-di-t-butyl)-5-chlorobenzotriazole;2-(2'-hydroxy-3'-t-butyl-5,
5'-methylphenyl)-5-chlorobenzotriazole;2-(2'-hydroxy-3',5'-di-t-butylphenyl)benzotriazole;2-(2'-hydroxy-5'-t-butylphenyl)benzotriazole;2-(2'-hydroxy-5'-octylphenyl)benzotriazole, of which 2-(2'-dihydroxy-5'-methylphenyl)benzotriazole and 2-(2'-hydroxy -5'-t-octylphenyl)benzotriazole (CyasorbTM)
5411) is preferred. From about 0.10 to about 0.50% benzotriazole with about 0.05 to about 1.0% organophosphite or organophosphonite, based on the weight of the glutarimide matrix polymer, is preferred.

ABS (acrylonitrile/butadiene/
It has been found that impact modifiers of the styrene) and MBS (methyl methacrylate/butadiene/styrene) types are useful in improving the impact strength of imide polymers while maintaining high service temperatures. Additionally, two-stage or three-stage core-shell all-acrylic impact modifiers are useful for improving the impact strength of imide polymers while maintaining high service temperatures. The ratio of impact modifier to imide polymer can vary over a wide range depending on how much impact strength improvement is needed for the particular application. The ratio of impact modifier to imide polymer is approximately 1
:99 to about 70:30 are useful, preferably about 5:
It is in the range of 95 to 60:40. Impact modifiers can be single or multi-stage polymers. For multistage polymers,
The impact modifier is a hard or soft first or “core”
It can have a step and then a step that can vary in hardness or softness.

From about 0.1 to about 25% by weight of flame retardants can be used, preferably compounds of bromine, chlorine, antimony, phosphorus aluminum trihydrate, organic compounds containing two or more hydroxyl groups, or It is a mixture of them. More specific examples of flame retardants include triphenyl phosphate, phosphonium bromide, phosphonium oxide, tris(di-bromopropyl) phosphate, cycloaliphatic chloride,
These are chlorinated polyethylene, antimony oxide, ammonium polyphosphate, decabromo-diphenyl ether and chlorinated polyphosphonate. The high service temperature of poly(glutarimide) in its base resin allows greater amounts of flame retardant to be added than to other base resins while maintaining an acceptable service temperature.

A wide variety of fillers can be used, with filler concentrations ranging from about 5 to 80%. Surprisingly, large amounts of fillers, such as hydrated alumina, up to about 60-70% can be blended with the glutarimide polymer base resin while maintaining thermoformability. On the other hand, most thermoplastic resin systems cannot have more than about 40% inert filler added while retaining thermoformability. The new imide polymers can be blended with glass fiber reinforcements having a glass concentration of about 1-60% to increase strength, stiffness, creep resistance and resistance to deformation at high temperatures, and to reduce the coefficient of thermal expansion. The compatibility of the glass fiber reinforcements with the new imide polymers is usually high and often allows the use of glass fiber reinforcements with standard coupling agents rather than specially manufactured reinforcements. Examples of reinforcing materials or fillers that can be used separately or in combination are glass fibers, polymer fibers, glass beads, titanium dioxide, talc, mica, clay, and the like. They may also be used in combination with other polymers that are compatible with them (ie, with which they can be blended, such as acrylics, poly(vinyl chloride), polycarbonates, polyesters, etc.).

The resulting polymer blend has a molecular weight of about 246 to
It can be molded at melt temperatures recommended for glutarimide polymers ranging from about 330<0>C, preferably from about 246<0>C to about 316<0>C, and most preferably from about 274<0>C to about 316<0>C. The polymer may be extruded into a film or formed into a parison and blown.
Alternatively, it may be compressed or injection molded into useful articles.

The plastics and polyglutarimides of this invention are also useful in applications such as sheets, films, molded articles or extrusions that do not require high transparency or visible light transmission. One such application is in automotive exterior lighting such as colored or tinted products such as yellow, red, orange, etc., such as colored taillights. A second use is in surface-modified products with matte finishes that reduce reflectivity and change contact behavior with other surfaces. Such products are manufactured by the use of certain inorganic fillers or by the use of U.S. Pat.
The use of surface-altering plastic additives with a similar refractive index as disclosed in US Pat.

[0030]

EXAMPLES The following examples are merely illustrative of the invention and are not intended to limit it. All percentages are by weight unless otherwise noted.

Plaque optical properties, ie yellowness index (YI) (ASTM D
-1925), % haze, and % total white light transmittance (% T
WLT) (both according to ASTM D-1003), 50.8 mm x 76.2 mm x 3.18 mm plaques were injection molded using a Newbury machine. The processing conditions are shown in Table 1.

[0032]

Table 1: (a) Barrel temperature of 282°C (b) Glutarimide with a degree of imidization of 90%:
Melting temperature 310-316℃

A. Polymer production and stabilizer incorporation (N
All exemplified polymers containing units of dimethylglutarimide (-methyl) and units of methacrylic acid were used as precursors of poly(
methyl methacrylate) and monomethylamine by methods known in the art. The reaction is about 66 or about 84 mole % (76 or 9
0% by weight) of either glutarimide unit. Next, some polymers are further reacted with dimethyl carbonate to form capped glutarimide (capp
de glutarimide). Uncapped glutarimide polymers contain polymethacrylic acid and glutaric anhydride functionality, while capped glutarimide polymers do not contain polymethacrylic acid and glutaric anhydride functionality.

The polymers of this study were prepared by reaction of a poly(methyl methacrylate) homopolymer with a MW of approximately 150,000 grams/mol with methylamine in a liquefied twin screw reactor. If a reduction in acid/anhydride content is desired (capped glutarimide polymer), the reaction with an acid/anhydride reducing agent was carried out on the polymer in a continuous manner. That is, without isolating the glutarimide polymer prior to the acid reduction reaction, the molten glutarimide is conveyed to an adjacent zone in the extruder and reacted there with the drug, after which the reduced glutarimide is transferred to the strands. It was isolated by heating, cooling and pelletizing.

A method of producing polyimide and reducing or substantially eliminating acid and anhydride functionality comprises removing a sample of the polyimide prior to reaction with an agent to reduce acid and anhydride functionality and It involves determining the amount of acid and anhydride in the polyimide prior to treatment with a capping agent by titrating the amount of acid and anhydride present. Next, add the amount of drug calculated based on the desired acid and anhydride concentrations. Alternatively, the amount of agent added may be determined by manufacturing the polyimide under the same conditions that may be used in a continuous process and then measuring the acid and anhydride concentrations. As long as the feedstock is converted to the same polyimide and treated with the drug under the same conditions, the final product produced is substantially the same.

The extruder used had a 2.0 cm (0.8 inch) non-interlocking
shing) is an inverted twin screw extruder (other sized extruders can also be used and they will give similar results). The extruder consisted of one section approximately 6 diameters long for introducing and plasticizing the polyglutarimide, followed by a closed barrel section approximately 6 diameters long for pumping and pressure generation; and a subsequent reaction zone. This zone, approximately 31.5 diameters long, consists of a ported barrel section for introducing blocking agent, a closed barrel section, and a vent section for removing volatile products. A separate vent section, operating at substantially atmospheric pressure, follows the reaction zone to remove additional volatiles. A larger extruder, such as a 5.0 cm extruder of the same design, may also be used and similar results will be achieved. The first (imidization) band is
It is 61 cm long and is equipped with means for adding solid polymer and methylamine. Example 1
The polymer feed rate was 72-75 grams/min. The barrel temperature in the imidization zone of Example 1 was 280
The temperature was ~300°C. Example 1 uses a 2.0 cm extruder (
Examples 2 and 3 contain data using a 5.0 cm extruder (2.0 inch). For the preparation of Example 1, Samples 1-13, methylamine was added at a rate of 26-32 grams/min and the gauge pressure was 6020-6060.
kPa; for the preparation of Example 1, Samples 14-29, the methylamine feed rate was 25-30 g/min and the gauge pressure was 6000-6200 kPa.
It was Pa.

Example 1, Samples 14-29 (uncapped glutarimide) were isolated at this point without further reaction. Samples 1-1 of Example 1
3 (capped glutarimide) was carried into the second zone as described above. Inside this zone, approximately 31 cm in length, there were means for adding acid reducing agents and venting volatile products. Another vent section allows for further devolatilization.
tion). Barrel temperature in the capping zone was 280-300°C. For samples 1-13 of Example 1, dimethyl carbonate (DMC) was
Added at a pressure of 5-3650 kPa; samples 1-1
For No. 3, the DMC feed rate was 8-10 cc/min.

In Example 2, the barrel temperature in the imidization zone was 260°C for samples 30-33 and 275°C for samples 34-37. The polymer feed rate for Example 2 was 240 lbs/hr. For the preparation of Samples 30-33 of Example 2, methylamine was added at a rate of 85-90 lbs/hr and the gauge pressure was 7475-7650 kPa. For the production of Samples 34-37 of Example 2, the methylamine feed rate was 79-80 lbs/hr and the gauge pressure was 761
It was 5 to 7650 kPa.

Samples 30-37 of Example 2 were conveyed into the second zone as described above. Inside this zone there were means for adding acid reducing agents and means for venting volatile products. Another vent section followed for further devolatilization. Barrel temperatures in the capping zone were 260<0>C for samples 30-33 and 275<0>C for samples 34-37 (no capping was applied for samples 34-37). For samples 30-33 of Example 2, dimethyl carbonate (DMC) was added at 5800-5890k.
It was added at a pressure of Pa. For samples 34-37 of Example 2, the nitrogen pressure in the capping zone was 4550
It was kPa. Regarding samples 30 to 33, DMC
The feed rate was 13.5 lbs/hr.

In Example 3, the barrel temperature in the imidization zone was 260°C for samples 38-41. The polymer feed rate was 240 lbs/hr. For the preparation of Samples 38-41 of Example 3, methylamine was added at a rate of 85-90 lbs/hr and the gauge pressure was 7475-7650 kPa.

Samples 38-41 of Example 3 were conveyed into the second zone as described above. Inside this zone were means for adding acid reducing agents and means for venting volatile products. Another vent section followed for further devolatilization. Barrel temperature in the capping zone was 260°C for samples 38-41. For samples 38-41 of Example 3, dimethyl carbonate (DMC) was added at a pressure of 5800-5890 kPa. For samples 38-41, the DMC feed rate was 13.5 lbs/hr.

In Examples 1-3, the plastic additive package (additive and phenylethylcyclohexyl ether) was carefully metered into the end of the extruder through the extruder addition inlet. In Examples 1-3, the plastic additive packages were preblended and then pumped into the extruder as a homogeneous mixture.

Example 1 This example shows the color (yellowness index:
This figure shows the effectiveness of various odor masking agents or fragrances according to ASTM D-1925).

[0044]

[Table 2]

[0045]

[Table 3]

Samples 1-7 (capped glutarimide): A) Additive package*: Stearyl alcohol 0.3% by weight
CyasorbTM 5411
0.25% by weight (3)
TNPP
0.15% by weight
Irisol
NTM 1.00 PPM (4
) B) The amount of odorant** was 100 PPM. Samples 8-13 (capped glutarimide):
A) Additive package*: Stearyl alcohol 0.3% by weight
CyasorbTM 5411
0.25% by weight
TNPP
0.15% by weight
Irisol NT
M 1.00 PPMB) The amount of odorant** was 200 PPM. Samples 14-21 (uncapped glutarimide): A) Additive package*: Stearyl alcohol 0.3% by weight
CyasorbTM 5411
0.25% by weight
Irisol NTM
1.00 PPMB) Odorant**
The amount of was 100 PPM. Samples 22-29 (uncapped glutarimide): A) Additive package*: Stearyl alcohol 0.3% by weight
CyasorbTM 5411
0.25% by weight
Irisol NTM
1.00 PPMB) Odorant**
The amount of was 200 PPM.

(1) PolyiffTM 1309
1 and PolyiffTM 41863 are Inter
nationalFlavors and Fragr
A fragrance blend of proprietary ingredients manufactured by Ances. (2) A negative yellowness index indicates that the sample is moving into the blue region. (3) CyasorbTM 5411 is Ameri
It is manufactured by can Cyanamid. (4) Irisol NTM is also Maxrolu
x Violet B, known as Mobay
It is manufactured by Chemical Company.

Example 1 demonstrates that the addition of PECE to glutarimide is preferred over other fragrances tested due to the better color (yellowness index) results exhibited by the addition of PECE.

Example 2 Odorant Rating Test (6 Participants) This example shows the evaluation of phenylethylcyclohexyl ether (P) in amine and/or ammonia odors in capped and uncapped glutarimide.
This shows the effect of ECE). An odor panel consisting of 6 participants evaluated 4 capped glutarimide samples (T-240) and 4 uncapped glutarimide samples (T-150), including 2 samples from each group. rated the unpleasantness of odors (based on the sense of smell) from best to worst (including PECE). Cinc the glutarimide sample
530 ~ by innati Milacron molding machine
Processed at 540°F. The melt drool from each sample was placed directly from the molder into a paint can. Each participant in the six-participant odor panel opened a randomly numbered can, sniffed its contents for approximately 3 seconds, and then immediately replaced the can with the next participant in the study. I sealed it. Odor ratings were rated anonymously among participants.

[0050]

[Table 4] Note: S = stearyl alcohol C = CyasorbTM 5411 770 = TinuvinTM 770 (Ciba Ge
igy) T = toner (Irisol NTM) PECE = phenylethyl cyclohexyl ether NS
DI = Name of experimental phosphite antioxidant manufactured by Uniroyal TNPP = Tris(nonylphenyl) phosphite

0
Odorant grade test results a) T-240 (capped):

[Table 5]

B) T-150 (uncapped):

[Table 6] Item: 1=Weakest amine and/or ammonia odor 4=
Strongest amine and/or ammonia odor

005
3. In general, participants found that samples 30-33 (capped glutarimide, T-240) were preferred by samples 34-3.
7 (uncapped glutarimide, T-150
) was noticed to have a milder odor (regardless of the presence or absence of PECE). These results indicate that PECE's uncapped glutarimide (
It is clear that the addition to T-150) provides advantages. For example, samples 36 and 37 (containing PECE) were easily distinguished by all six odor panel participants as more desirable and pleasant odors from samples 34 and 35 (containing no PECE).

EXAMPLE 3 This example deals with capped glutarimide (T-240) generated under harsh processing conditions (530-540°F).
) Phenylethyl cyclohexyl ether (PEC) in amine and/or ammonia odor in polymers
This shows the effect of E). The following samples were processed using a 2.5-inch Prodex extruder with a two-stage screw and a 24-inch Johnson sheet die.
Extruded at ~540°F. The samples were ranked from best to worst by molding test participants.

[0055]

Table 7 Item Rating: 1 = Weakest Amine and/or Ammonia Odor 4 = Strongest Amine and/or Ammonia Odor Additive Package (wt%): S = Stearyl Alcohol (0.3%) C = Cyaso
rbTM 5411 (0.11%) C*=Cyasor
bTM 5411 (0.25%) 770 = Tinuvi
nTM 770 (0.12%) T = toner (e.g. Ir
isol NTM ) (1 PPM) PECE = phenylethyl cyclohexyl ether (500 PPM) TNPP = tris(nonylphenyl) phosphite (0
．． 15%)

Claims (31)

[Claims] [Claim 1] A plastic and the following structural formula [Claim 1]
A polymer composition consisting of phenylethylcyclohexyl ether having the formula: wherein R1, R2, R3 and R4 are the same or different substituents selected from methyl or hydrogen. 2. The polymer composition according to claim 1, wherein the plastic is a polyglutarimide or a (meth)acrylic copolymer. [Claim 3] Poly(glutarimide) is poly(N-
lower alkyl) dimethylglutarimide or poly(N
-hydrogen) dimethylglutarimide. 4. The composition of claim 3, wherein the poly(N-lower alkyl)dimethylglutarimide is poly(N-methyl)dimethylglutarimide. 5. The composition of claim 2, wherein the amount of phenylethyl cyclohexyl ether is from about 0.01 to about 1.0% by weight of the polymer. 6. The composition of claim 2, wherein the amount of phenylethyl cyclohexyl ether is from about 0.01 to about 0.10. 7. Further, at least one selected from toner, lubricant, antioxidant, colorant, ultraviolet stabilizer, ultraviolet light stabilizer, impact modifier, pigment, filler, fiber, and flame retardant. The composition according to claim 1, containing an effective amount of the additive. 8. The composition of claim 7, wherein the lubricant is a long chain alkyl ester of a high molecular weight alcohol or high molecular weight acid. 9. The composition of claim 7, wherein the lubricant is stearyl alcohol. 10. The amount of lubricant is about 0.05% of the polymer.
9. The composition of claim 8, wherein the composition is about 0.50% by weight. 11. A composition according to claim 7, wherein the UV stabilizer is benzophenone, salicylate ester or benzotriazole. 12. The composition of claim 7, wherein the ultraviolet light stabilizer is a hindered amine. Claim 13: The hindered amine is bis(2,2,
13. The composition according to claim 12, which is 6,6-tetramethyl-4-piperidinyl)-sebacate. 14. The composition of claim 11, wherein the UV stabilizer is 2-(2'-dihydroxy-5'-methylphenyl)benzotriazole and 2-(2'-hydroxy-5'-octylphenyl)benzotriazole. thing. 15. The composition of claim 11, wherein the amount of UV stabilizer is from about 0.10 to about 0.50% by weight of the polymer composition. 16. The impact modifier is selected from one or more of acrylonitrile/butadiene/styrene and methyl methacrylate/butadiene/styrene.
Compositions as described. 17. The composition of claim 7, wherein the impact modifier is a two- or three-stage core-shell all-acrylic impact modifier. 18. The weight ratio of impact modifier to polymer is from about 5:95 to about 60:40.
Compositions as described. [Claim 19] The antioxidant is phenol, amine,
8. The composition of claim 7 selected from the group consisting of phosphites or thioesters. 20. The composition according to claim 19, wherein the phosphite is an organic phosphite or an organic phosphonite. 21. The composition of claim 20, wherein the organic phosphite is tris-(nonylphenyl) phosphite, distearylpentaerythritol or tris(2,4-di-t-butylphenyl) phosphite. [Claim 22] The organic phosphonite is tetrakis(2
, 4-tert-butylphenyl) 4,4'-biphenylene diphosphonite. 23. The composition of claim 19, wherein the amount of phosphite is from about 0.05 to about 1.00% by weight of the polymer composition. 24. The composition of claim 7, wherein the fillers are hydrated alumina, glass fibers, polymer fibers, carbon fibers, glass beads, titanium dioxide, talc, mica, and clay. 25. The composition of claim 7 blended with a (meth)acrylic, poly(vinyl chloride), poly(amide), polycarbonate, polyester, SAN, ABS, MBS polymer or all-acrylic impact modifier. Composition. 26. The flame retardant is triphenyl phosphate, phosphonium bromide, phosphonium oxide, tris(dibromopropyl) phosphate, cycloaliphatic chloride, chlorinated polyethylene, antimony oxide, ammonium polyphosphate, decabromo-diphenyl ether and chlorinated polyphosphonate. 8. The composition of claim 7. 27. For masking plastics and undesirable odors, the following structural formula: [Image Omitted] wherein R1, R2, R3 and R4 are the same or different substituents selected from methyl or hydrogen. A polymeric composition comprising an effective amount of phenylethylcyclohexyl ether having the following properties: 28. Poly(glutarimide) and phenyl having the following structural formula: where R1, R2, R3 and R4 are the same or different substituents selected from methyl or hydrogen. A method of masking the amine and ammonia odor of poly(glutarimide) by mixing ethylcyclohexyl ether. 29. Poly(glutarimide) and phenyl having the following structural formula: where R1, R2, R3 and R4 are the same or different substituents selected from methyl or hydrogen. A method of masking the amine and ammonia odor of poly(glutarimide) by mixing ethyl cyclohexyl ether and at the same time not producing undesirable colors. 30. A product in the form of a sheet, film or molded article produced from the composition of claim 1. 31. A product in the form of a sheet, film or molded article produced from the composition of claim 27.