AU606641B2 - Condensation copolymers containing bis-methine moieties and products therefrom - Google Patents

Description

I

w

AUSTRALIA

Patents Act 606641 COMPLETE SPECIICKATION

(ORIGINAL)

Class Int. Class Application Number: Lodged: Complete Specification Lodged: Accepted: Published: Priority Related Art: This documnen', Contains the amendments made u~ld.!r S ,Cction 419 und is correct for Pintting, APPLICANT'S REF.: Docket No. 51,109 IName(s) of Applicant(s): Address(cs) of App!xant(s): EASTMAN KODAK COMPANY 343 State Street, Rochester, New York 14650 UNITED STATES OF AMERICA MAX ALLEN WEAVER CLABERNCE A.LVIN COATES, JR WAYNE PAYTON PRUETT SAMURL DAVID HILBERT

S

Actuli inventor(s): Address for Service is: PHILLIPS, ORMONDE AND FITZPATRICK( Patent and Trade Mark Attorneys 367 Collins Street Melbourne, Australia, 3000 Complete Specification for the invention entitled, CONDENSATION COPOLYMERS CONTAINING BIS-METH-INE MOIETIES AND PRODUCTS THEREFROM The lollowing statenlert Is a full description of this invention, including the best method of performing it known to applicant(s): 1,19A!84 i S- li- Description Condensation Copolymers Containing Bis-Methine Moieties and Products Therefrom Technical Field -This ap-l3&a-i-&n is a conti-nua-t4-on-in-part of -~our co-pending Application Serial No. 947 S *December 29, 1986.

0 This invention concerns condensation polymers .including linear polyester, unsaturated polyester, 10 and polycarbonate types, wherein certain bis-methine moieties have been copolymerized (condensed) into the polymer to impart UV screening thereto. The bismethine moieties are thermally stable and nonsublimable at the polymer processing (includes 15 preparation) temperatures, are nonextractable therefrom, do not discolor the polymer, and absorb radiation over the entire harmful wavelength, thus f rendering the polymers particularly suitable for use as beverage bottles and food, pharmaceutical and 20 cosmetic containers. The bis-methine moieties are .0 useful in total concentrations (of single moiety or mixtures thereof), given herein in parts per million (ppm), ranging from about 1.0 to about 10,000, preferably 2.0 to about 1,500 ppm, and most preferably from about 100 to about 800 ppm (parts by weight of moiety per million parts by weight of final polymer).

Background Art Heretofore, various UV absorbers such as the benzophenones, benzotriazoles and resorcinol monobenzoates have been incorporated into polymers as discussed in Plastics Additives Handbook, Hanser 2 1

I,

-2- Publishers, Library of Congress Catalog No.

83-062289, pp 128-134, for use in absorbing or screening deleterious radiation. The additives function well to screen radiation in the range of from about 300 to about 350 nm, however, this range is not adequate to protect the contents of food packaging employing these polymers. Moreover, these compounds when added to polyesters are extrac-able by solvents which may be present in food packaged with 10 the polymers. Such solvents would include typical food acids, alcohols and the like. Furthermore, these compounds are not in general stable under the polyester manufacturing and processing conditions and produce objectionable yellow shades in food packaging. Also, the various copolyesters such as disclosed in U.S. Patent 4,338,247, while having

C.

essentially nonextractable UV absorbers, are not suitable for food packaging in that the absorbers transmit harmful radiation and are not designed to 20 protect food.

U.S. Patent 3,634,320 discloses compounds somewhat similar to applicant's for mixing into various polymers for U.V. absorption, however, S. copacymerization is not involved and the max values for the compounds are not sufficiently high to protect food. It is noted that the polyiunctional compounds of the patent would act as cross-linking agents in any attempted copolymerization.

Disclosure of Invention The present linear polymers are thermoplastic molding or fiber grade 4 hdving an I.V. of from about 0.4 to about 1.2, and preferably are polyesters wherein the acid moiety is comprised of at least about 50 mol terephthalic acid residue, and the glycol moiety at least about 50 mol ethylene glycol I i" 3 or 1,4-cyclohexanedimethanol residue, and containing a total of from about 1 to about 10,000 ppm of one or a mixture of the bis-methine moieties. The term "acid" as used herein with respect to both the linear and unsaturated polyesters includes their various reactive derivatives such as dimethylterephthalate, anhydrides and the like. A highly preferred polyester within this preferred group is comprised of from about 75 to 100 mol terephthalic acid residue 10 and from about 75 to 100 mol ethylene glycol oc residue.

In accordance with the present invention, the bis-methine moieties derived from the reactants shown below impart to the polymers the property of ultraviolet absorption generally significantly within the range of from about 250 nm to about 390 nm, and have their maximum absorbancies in the 340-350 nm range.

The moieties preferably have molecular weights of i 9.

from about 280 to about 400 although lower or higher 20 molecular weights are also operable and are derived from reactants (monomers) having one or more groups which condense during condensation or polycondensation to enter the moiety into the polymer chain.

S.a. These groups include hydroxyl, carboxyl, carboxylic ester, acid halide and the like. As aforesaid, these moieties are thermally stable at polymer processing conditions, which includes polycondensation temperaturc- of up to about 300°C which are used, for example, in the preparation of polyesters such as poly(ethyleris terephthalate) and copolymers of terephthalic acid, ethylene glycol, and 1,4-cyclohexanedimethanol.

It is pArtti!ularly noted that when the levels of the present ultra-violet light absorbers are increased to higher levels such as 5,000 ppm or -4higher, polymers containing these ultra-violet light absorbers show improved resistance to weathering and when the'se polymers per se or fibers thereof are dyed with disperse dyes, at a concentration, for example, of from about 0.01 to about 5.0% based on weight of polymer or fiber, many dyes exhibit increased lightfastness. Such disperse dyes are shown, for example, in U.S. Patents: 4,30S,719 2,746,952; 2,746,953; 2,757,173; 2,763,668; 2,771,4~66; 2,7/3,054; 2 ,7 77 ,8 6 3; 2,785,157; 2, 790 ,791 2,798,081; 2,805,218; 2 ,822 ,359 2,821,450; 2,832,761; 2,852,504; 2,857,371; 2, 865 ,909; 2,871,231; 3 ,0 72 ,6 8 3; 3 ,0 79 ,3 73 3 ,079 ,375; 3, 087,773; 3,096,318; 3,096,322; 3,236,843; 3,254,073; 3 ,3 49 ,0 7 5; 3,380,990; 3,386 ,990 3,394,144; 3,804,823; 3,816,388; 3,816,392; 3,829,410; 3,917,604; 3,928,311; 3 ,9 80 ,6 2 6; 3,998,801; **4,039,522; 4 ,052, 379 and 4,140,683, the disclosures of which are incorporated herein by reference.

20 The present invention is defined iLn its broad embodiment as a composition comprising molding or fiber grade condensation polymer having copolymerized therein a total of from 1.0 to about 10,000 ppm, of :the reactant residue moieties of one or a mixture of bis-methine reactants of the formula M I=HC-Ar I -CH-M 2 '6 wherein 1 Ar is an unsubstituted or substituted 1,4-phenylene radical; and M 1 and M 2are the same or different and each is a disubstituted methylene group having the structure 1 2 NG-9 or R3_M wherein 3

R

1 is R- 0-R X-l, 4 SO 2 -X-R 2_ 4; or -Ar 2 -R and 2s~.X 4 2 R2 is X-R or -Ar2 -R wherein

R

3 is hydrogen, ally1 or an unsubstituted or substituted alkyl, cycloalkyl or phenyl radical; X is a divalent alkylene, cycloalkylene or 10 phenylene radical or a combination thereof which may include within the divalent chain one or two atoms or 3 3 radicals selected from -S02, N- or S 15 0 1

R

IX

R

wherein 6 R is an unsubstituted or substituted alkyl, cycloalkyl or phenyl radical; R is a group that is reactive with one of the Ar t 20 monioners from which the condensation polymer is prepared; 2 Ar 2 is an unsubstituted or subs'ituted phenylene or heteracyclic arylene radical;

R

5 is hydrogen, R 4 or -X-R 4 wherein the bis-methine moiety absorbs radiation significantly in the range of 250 to 390 nm and is non-extractable from said polypsr and is stable under the conditions the polymer is prerared Or processed.

1 The 1,4-phonylene radical represented by Ar the phenylene rodical which Ar and X can represent, the phenyl radical which R3 can represent and the heterocyclic arylene radical which Ar 2 can represent may be substituted with up to four -7

U

it -6 44 4 4 4 4S*4 4.4.

4 9eS*94 64 44 4 4 9, 4 9 q 4.

9 4.9 4* 9 .4 49 4 94 9.

64444 9 substituents selected from lower alkyl or halogen.

As used herein to descrtbe an alkyl or an alkyl moiety-containing group, "11cwerl" designates a carbon content of up to 4 carboii atoms.

T4he alkyl radi -as represented R 3and R6 may contain from 1 to 8 carbon atoms and may be sut-stituted with one or more substituents such as hydroxy, lower alkoxy, lower hydroxyalkoxy, lower alkanoyloxy, lower alkanoylamnino, cyano, halogen, 10 furyl, tetrahydr'ofu-Cyl, lower alkoxycarbonyl, lower alkylsulfonyl, carbamoyl, N-alkylcarbamoyl, N,Ndial kyl carbanoyl, pheny'L, lower alkylphenyl, lower alkoxycarbo, iylphenyl, halophenyl and the like. The alkyl group represented by R 3and R 6preferably are unsubstituted lower alkyl.

The cycloalkyl groups which R 3and R 6can represent pr~eferably are cycloalkyl of 5 to 7 carbon atoms such as cyo'lopentyl, cycloheptyl and, especially, cyclohexy.b, Such cycloalkyl groups may 20 be substituted with up to four substituents such as lower alkcyl, lower alkoxy, halogen, lower hydroxyalkyl, lower alkoxycarbonyl -,nd the like. The phenyl radicals which R 3and R 6c'c&n represent likewise may be substituted with the substituents whitch may be pre'?,ent on the substituted alkyl and cycloalkyl xadicals described n~reinabove.

The diva)-snt group represented by X may be selected from a wide variety of alkylene, cycloalkylena and phenylene radicals or combinations thereof containing a total of up to 12 carbon atoms.

The alikylene groups may contain up to 8 carbon atoms and may contain within their chain hereto atoms such as oxygen, sulfur and nitrogen and/or cyclic groups such as cycloalkylene or phenylene radicals. Example of the group represented by X include alicylene, Oe -7alkylene-O-alkylene, alkylene-SO 2-alkylene, alkylene-S-alikylene, alkylene--- L-alkylene, alkylene--O-a1Acylene-O-alk.ylene, alkylene S alkylene, alkyleni:--O--!'-S \.O-alkylene, al1ylene 2 1-alkylene, O-alkyl OQ-pheny1 alkylene-M~-alkylene, alkylene-al1'ylene, qO 2-phenyl henyl alkylene-h-alkylene, alkylene-N.alkylene,

V.

NH-phenyl NH-phenyl alkylenei -alkylene, alkylene- -lyee alkyene ineNH-cyclohexyl en- kye, alkylenei-*alkylene, arylerie, oi' cyclohexylene. The divalent group represented by X preferably is alkylene of 1 to 4 carbon atoms, cyclohexylene or phenylene.

The reactive group represented by R' may be 6 p .hydroxy, an ester group such as -0~ or NHR wherein is defined hereinbove, carboxy, carbonyl halide such as carbonyl chloride or amino. Such reactiVe groups represented byR may Ibe attached directly to divalent radical X or Indirectly through various bridg;ing groupso e.g., hydroxyalkoxyalkyl, hydroxyAlkyl, acetoxyalkoxy, N-hydroxyalkylsulfal~foyl, etc. XIt Is apparent that the ester groups 1_j.6 1 arid cJNH- R 6 and the substituents represented by R3and R 6 in the groups I ~i ~L1 I: I a-R and O-R6 are displaced or removed from the bis-methine compounds upon reaction with the polymer or polymer precursor. Thus, those residues are not an important part of the bis-methine residue component of our novel compounds.

The heterocyclic arylene groups represented by Ar2 may be substituted with one or more lower alkyl or halogen substituents in addition to being 10 substituted with a reactive R 4 substituent. The g*e C heterocyclic group may be selected from one of the groups having the structure 64 some R 54 tt-Rf R tt-R

S

.J3 I-l .5 -V-h 5 5 R#-R or U R C which, as mentioned above, may be also substituted with lower alkyl and/or halogenr Of particular interest are condensation polymers containing the residue of a bis--methine compound having the formula 1-.1 (6)1-4 wherein R 3 is defined above and R 8 is hydrogen, 8 alkyl or halvgen. Compounds in which R is 3 hydrogen and R is alkyl oF 1 to 6 capto atom are particularly preferred.

-9- A second group of preferred compounds have the formula ~8 )n wherein R slower alkoxycarbonylphenyl, lower 4loyabnlezyloe loyabnl2 10 benzoxazolyl, lower alkoxycarbonyl-2-benzothiazolylo Vto: lower alkoxycarbonyl-2-benzirddazolyl, N-lower ~''*hydroxyalkylcarbamoyl or N-lower alkanoyloxy- lower- .*alkylcarbamoyl;, R 8is lower alkyl, halogen or, most preferably, hydrogen; and is. I or 2.

A third group of preferred compounds have the to formula 'P2 2 3 34 wherein 3 R is lower alkyl; R 2is benzoyl, 2-benzoxazolyl, 2-benzothiszolyl or 2-benztrnidazoly1,, R 8 is lower alkyl. halogen ori most preferably, hydrogen; and n is I or 2.

3a The bis rnethine compounds used In the preparation of the novel polymer compositions provided by thia inven~tion may be pr'epared by the krioevenagel reaction whereby a bis-aldehYde is condensed with an active methylene compound i the presence of a base such as piperidine or sodium acetate as shown by the follow~ng reaction scnemcs:~ 1 1 OHC-Ar I-CHO NCC ae .N-=C-Ar I C= -CN III IV I 0HC--Ar 1 CHO R -J0-CH 2 ae aIII IV 22 10 3 44 a 0 it Typical alcehydes III are terephth laldehyde, 2-chloroterephthalaldehyle, 213-dichloroterephthalalclehyde, 2--fluoroterephthaleldehyde# 2-nethylterephthalalidehyde, phthalaldehyde, 205-dimethylterephthaldehy(e, and 94. ,*tetramethyl terePhthalaldehyde. Suitable cyanonaetic Pold esters are, for example, methyl cyanoacetateo 20 ethyl cyanoacetate, lSopropyl cyanoacetate, rh-butyl cyanoacetatet dyclohexyl cyarioacetatei bebZYl cyanoacetates phenyl cyanoacetatet 2-hydroxyethyl cyani acetate# 2--methoxyethyl cynnoacetate 1 2-chloroethyl cyanoacetate, n--heXyl cyantoacetate, sec butyl cyancacetate, tert-butyl cyanoacetato) Methy! 4-(cyano methyl)benzoate, ethyl Z- (2-benzoxazolyl)acetate, ethyl 2-bonzoylacetate, etc..

The tnonextroctabilitie8 of the rgn bia-imethino moieties are determined a~s follows: 11 Extraction Procedure All extractions are done in glass containers with distilled solvents under the time and temperature conditions described below. The sample form is 1/2 inch x 2-1/2 inch segments cut from the cylindrical side wall portion of 2-liter bottles.

All samples are washed with cold solvent to remove surface contaminants and are exposed using 200 ml.

2 2 solvent/100 in. surface area (2 ml/in. Solvent blanks are run under the same extraction conditions without polymer. In most cases samples ere extracted, spiked, with a known amount of additive as a contrcl, and analyzed in duplicates.

m Extraction Conditions 1. ater The samples at room temperature are added to solvent and heated at 250OF for two hours.

Half L the samples are then analyzed and the Lemainder are placed in a 120 0 F oven for 30 days.

2, 50% Ethanol/W:ter. The samples at room temperature are added to the solvent at room tempera.

ture, placed in an oven at 120 0 F and analyzed ifter 24 hours and 3Q days.

3. Heetane. The samples at room temperature arG added to solvent at room temperature and heated at 150 0 F for two hours. Part of the samples are cooled to room temperature and analyzed spectrophotometrically and the remainder are allowed to age at 120F for 30 days before analysis.

4. Any suitable analytical technique and apparatus may be employed to determine the amount of bis-methine moiety extracted from the polymer.

The extractability of the present bis-mcthine moieties from the present polymers was found to be essentially nonexistent, 12 Polyesters useful in this invention include linear, thermoplastic, crystalline, or amorphous materials, produced by conventional techniques using one or more diols and one or more dicarboxylic acids, copolymerized with the bis-methine moieties.

Also useful are the unsaturated, curable polyesters which are the polyesterification products of one or more dihydric alcohols and one or more Sunsaturated dicarboxylic acids or their anhydrides, 10 and the term "polyester resin" is used herein to i define the unsaturated polyester dissolved in or Sadmixed with an ethylenically unsaturated monomer.

Typical of the unsaturated polyesters is the polyesterification product of 1,4-cyclohexane-

U.

15 dimethanol and/or 2,2-dimethyl- ,3-propanediol and optionally an additional dihydric alcohol, such as ethylene glycol, and maleic acid or fumaric acid and an unsaturated hydrogenated aromatic dicarboxylic acid, which when crosslinked with an ethylenically- 20 unsaturated monomer, styrene, produces a cured I polyester resin which has, for example, high thermal resistance, high heat distortion values, excellent electrical and mechanical properties, and excellent 25resistance to chemicals.

25 The unsaturated polyester resins may be prepared in the presence of gelation inhibitors such as hydroquinone or the like, which are well known in the art of polyesterification. The esterification may be carried out for example under an inert blanket of gas such as nitrogen in a temperature range of 118 0 -220C for a period of about 6-20 hours until an acid number below 100 and preferably below 50 is obtained, based on milliequlvalents of KOH necessary to neutralize 1 gra.n of the Unsaturated polyester. The resulting polyester may be subsequently copolymerized, cross- 13 6 em 0 0 v 4.

5

SO

SS

S S

S.

S *5

S

4 S.

S

linked, or cured with "curing amounts" of any of the well-known ethylenically unsaturated monomers used as solvents for the polyester. Examples of such monomers include styrene, alpha-methyl styrene, vinyl toluene, divinyl benzene, chlorostyrene, and the like as well as mixtures thereof. Typically, the mole ratio of such unsaturated monomer to the unsaturated moity maleic acid residue) in the polyester is from about 0.5 to about 3.0, although the "curing 10 amounts" of such monomer can be varied from these ratios.

It is preferred that the unsaturated polyester be prepared from one or more dihydric alcohols, fumaric or maleic acid or mixtures thereof, and up to 15 about 60 mole percent of total acid component of o-phthalic, isophthalic or terephthalic acids or mixtures thereof. Preferred for the dihydric alcohol component is one or a mixture of propylene glycol, neopentyl glycol, 2,2,4-trimethyl-l,3-pentanediol, ethylene glycol, or diethylene glycol. A specific preferred unsaturated polyester is prepared from about 75 to 100 mol propylene glycol, and as the acid component, from about 75 to 100 mol o-phthalic and maleic acids in a mole ratio of from about 1/2 to 25 about 2/1. Typical of these unsaturated polyesters are those disclosed, for example, in U.S. Patent 4,359,570 incorporated herein by reference.

The diol components of the linear polyester are selected, for example, from ethylene glycol, 1,4-cyclohexanedimethanol, 1,2-propanediol, 1,3propanediol, 1,4-butanediol, 2,2-dimethyl-1,3propanediol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, X,8-bis(hydroxymethyl)tricyclo-[5.2.1.0]-decane wherein X represents 3, 4, 1 L i i(-i(i II- 14 or 5; and diols containing one or more oxygen atoms in the chain, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol and the like. In general, these diols contain 2 to 18, preferably 2 to 12 carbon atoms. Cycloaliphatic diols can be employed in their cis or trans configuration or as mixtures of both forms.

The acid components (aliphatic, alicyclic, or aromatic dicarboxylic acids) of the linear polyester 10 are selected, for example, from terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, 1,12- S* dodecanedioic acid, 2,6-naphthalene-dicarboxylic acid 15 and the like. In the polymer preparation, it is often preferable to use a functional acid derivative thereof such as the dimethyl, diethyl, or dipropyl ester of the dicarboxylic acid. The anhydrides of these acids also can be employed where practical.

The preferred linear copolyesters are especially useful for making blow molded bottles or containers for beverages, and for molded food packages and the like. In this regard, certain of these copolyesters 6e*U are color, and heat distortion or "hot fill" 25 stable at temperatures of up to about l0o0C., when properly heat set and molded articles therefrom exhibit good thin wall rigidity, excellent clarity and good barrier properties with respect to water and atmospheric gases, particularly carbon dioxide and oxygen.

In regard to products having the "hot fill" stability, the most preferred linear polyesters therefor comprise poly(ethylene terephthalate) and this polymer modified with up to about 5 mole of 1,4-cyclohexanedimethanol, wherein the polymers have s 15 been sufficiently heat set and oriented by methods well known in the art to give a desired degree of crystallinity- By definition, a polymer is "hot fill" stable at a prescribed temperature when less than 2% change in volume of a container manufactured therefrom occurs upon filling the same with a liquid at that temperature. For the particular application of blow-molded beverage bottles, the most preferred polyesters have an I.V. of 0.65 to 0.85, and a Tg of 10 >70°C, and film sections cut from the bottle have a Water Vapor Transmission Rate of 1.5 to 2.5 g.

2 mils/100 in. -24 hrs., a CO2 Permeability of 2 20-30 cc. mils/100 in. -24 hrs.-atm., and an 0 2 Permeability of 4-8 cc. mils/100 in.2-24 hrs.-atm.

15 The Tg is determined by Differential Scanning Calorimetry at a scan rate of 20 Centigrade Degrees/min., the 0 Permeability by the standard 2 operating procedure of a MOCON OXTRAN 100 instrument of Modern Controls, Inc., of Elk River, Minnesota, and the CO 2 Permeability by the standard operating procedure of a MOCON PERMATRAN C II, also of Modern Controls.

Typical polycarbonates useful herein are disclosed in Kirk-Othmer Encyclopedia of Chemical 25 Technology, third edition, Volume 18, pages 479-494, incorporated herein by reference.

The inherent viscosities of each of the copolyesters herein are determined according to ASTM D2857-70 procedure in a Wagner Viscometer of Lab Glass Inc. of Vineland, N.J. having a 1/2 ml capillary bulb, using a polymer concentration of by weight in 60/40 by weight, phenol/tetrachloroethane solvent. The procedure comprises heating the polymer/solvent system at 120°C for 15 minutes to enhance dissolution of the polymer, cooling the 16 solution to 25 0 C and measuring the time of flow at The I.V. is calculated from the equation 25 0 C s i] in 0.50% -C where: Inherent viscosity at 25°C at a polymer concentration of 0.5 g./l00 ml. of solvent; Sin Natural logarithm; 10 t s Sample flow time; to Solvent-blank flow time; and C Concentration of polymer in grams per 100 ml. of solvent 0.50.

Best Modes for Practicing The Invention EXAMPLE 1 f Terephthalaldehyde (2.68 g, 0.02 methyl cyanoacetate (4.0 g, 0.04 methanol (50 ml), and piperidine acetate (0.5 g) are mixed and heated at reflux for one hour. The reaction mixture is cooled 20 and the solid product is collected by filtration, S: washed with methanol, and dried in air. The product, dimethyl 3,3'-(1,4-phenylene)bis-.[2-cyano- 2j propenoate], weighs 2.2 g and has a maximum in the UV absorption spectrum in acetone at 345 nm with an extinction coefficient of 36,704.

EXAMPLE 2 A mixture of terephthalaldehyde (0.67 g, 0.005 mol), methyl 4-(cyanomethyl)benzoate, ethanol mL), piperidine (10 drops) and acetic acid (5 drops) is heated at reflux for four hours. The reaction mixture is cooled to precipitate the product which is I

I

17 collected by filtration, washed with ethanol and dried in air. The yield of product is 1.1 g. Mass spectroscopy confirms the product is the expected 3,3'-(1,4-phenylene)bis-[2--(4-methoxycarbonyl)phenyl-- 2-propenenitrile] having the structure: 3* 3 H CH 3 EXAMPLE 3 A mixture of terephthalaldehyde (1.34 g, 0.01 0* 10 mol), ethyl 2-(a-benzoxazolyl)acetate (4.10 g, 0.02 mol), ethanol (20 ml), piperidine (10 drops) and acetic acid (5 drops) is heated at reflux for three hours. The product crystallizes during the period of heating and is collected by filtration of the hot 1 15 reaction mixture. The product obtained is washed with ethanol and dried in air to yield 3.5 g of product which analyses confirmed is diethyl 3,3'- (1,4-phenylene)bis-[2-(2-benzoxazolyl)-2-propenoate] having the structure: -CH=C

N

C

2 H 5 Og OC2 H Additional examples of bis-methine compounds which may be used in the preparation of our novel polymer compositions are set forth in the following tables.

These compounds may be prepared according to the procedures described in the preceding examples and conform to the generic formulas given for each table.

mmm -18- TABLE I 14- -C 1\C -i Ex. R 1

R

5 -COOCHC H H -COOCHCH(CH )c H 7 -COOCH 2CH2 HC32H 00*1 10 8 COOC (CH3)3 H 0 0 9 -COOCHC 6 H1 H -COOC H -4-OH H 6 4 3 :11 -GOOC 6 H H 12 -COOC 5 H 9

H

13 -COOCH 2 CHCH C H 14 -COOCH 2 H C 2 3 bH

-COOH

2 6 l 19 4 44 4 4 444 4 4~4* 4 444444 4 44 *4 4 4 4 .4 4 4 4 444 .4 4 4 44 4. 4 64 4 4*C4*4 .4 44 4 44 4 4 4.

.4 Ex.

16 3:' 18 19 20 21 22 23 10 2'4 25 26 27 28 29 31 32 -C00u'I 2 rH 2GH -COOCI2 CH 2Cl -COOCH 2CH 00c H5 -COH2 CH2 2c6H5 -COOCH 2C 6H lo C H O 2-OOC 25 -COOC H -COOCH C3

A-HO

-COOCH

2

CH

-COOC

C

-C OOCH -COOCH 3 -COH2 CH2 cc2 H5 COOCH 2 CH 2 NHCOCH 3 -COH2 CH2000CH 3

H

H

H

H

H

H

H

2-C

H

3 2--Cl 2, 5-d i-CH 3 2-F 2, 3-di-Cl 2, 5-di- Cl 2,3,5,6-tetra CH 3

H

H

H

Ex. RR 33 -COOC- CH(OH)CH OH H 2 2 34 -COOC H -4-C HH 6 10 2 -COOCH CH=CH H 2 2 36 -C H -4-COOCH 6 4 3H 37 *38 H N-CH-(5--COOC 2

H

5

H

39 H -(5-COOCH 3

H

2 2* 10 40 -SON2C 1H 4CH 2 H2OHH 4 -SO 2 C H 4 -1 41-COCHO-H 42 OHC H O-O NHHCHO H 63 3 2 2 46 _NN-C (COON H 21- Ex. RR 47 -SO 2 CH 2CH OCH 2H OH H 48 CONHCH C 6 H 0-4-OH OH H 49 CONHCH 2CH C6 H -4-4COOCH 3

H

50 -CONHCH CH-2 SCH CH-2 OH H 51 '-CONHCH 2, CH OOCCH 52 SO 2

CH

2

CH

2 00COC H H 53 CON-iC CH H -4-COOH H 2 6 54 -C H -4-COCI H 6 4 55 6 3-(5-SO 2NHCH 2 CH 2OH)-Q o f* a 58 -C 6 H 4 4-CONH(CH 2 CH 2 0) 2 H 2-CH 3 2 2 ee I S S S S

S.

S

.5 S..

S..

S.-

a a a a. S S

S

a a S a S *55 S TABLE I I Ex -COG H5 -C -C 2H 61 -FN 6' 62 -No- 6H3 6C 3) rH 3 63 -ANoC6f 64 -C 6 i -4-CN =NCH(C 6

H

5 )=Cl -CH.2" CH 3l -CH 2=CH~ -CH C UH=CH OH 66 =N-o-C 6 H 3 5-COOI{ 3 67 =CHCH=C(CH 3 b H2 c6 1OC 2 O -CH 2 c 6 A A A A A* a 1 A A, ,68 i6 .NHCCH 69 (Y N-o-c 6 6-SO 2 N (C 3) 71 -C 6H4-4-SO NHCHf 72 -C6 H 4 -4-so 2 CH 3 73 -COG 6 I4 -4--CQCH3 74 COG 6H 3-3,4-di-Ci tY=CHCH=G[SQ 2

N(CH

3 2

A

76 -C 6H 3-3-SQ NHCH 2CH 011f-4-0GB 77 COG 6 1fH 4 -4--COOCH 3 a.

0 A, A A. A -CH CH 2

C

6 11 CH 2

HC

2 2

H

-C 2H5 -C 2H5 2, 5-di--C

G

3 2 ,5-di-C1 -CH 3

CHCH

2 SCH CH 01- C22

CAH

2-CH 3 78 0- 1 0 4

-CH

3

MON.-

go aCCH 2 H 5 2 H H a EXAMPLE 81 The following compounds are placed in a 500-mi, thiee-necked, round-bottom flask: 97 g (G.5 mol) dimethyl tI rephthalate; 62 g (1.0 mol) ethylene glycrwl; 0.064 ml of a n-butanol solution of acetyl,-triisopropyl titanate which contains 0.00192 g TA; 1.1 ml of an ethylene glycol solution of Mn (OCOCH. 3 2 4H 2 0 which contains 0.0053 e, Mn; 2.3 nil of an ethylene glycol solution of Sb(QCOCH 3 which contai~ns 0.0216 g Sb; and 0.64 ml of an ethylene glycol, solution of Co(QCOCH 3 2 -411 2 0 which contains 0.0072 4, Co.

The flask~ is equi,, ped with a nitctz'gen inlet, stirrer, vacuum outlet, and condensing flask. TheP flask and co'ntents are hea_* J at 2o00 0 C in a Belmont 20 metal bath for 60 minutes and at 210"IC for 759 minutes with a nitrogen sweep over the reaction ntixture.

*Then 1.57 ml of an ethylene glycol slurry of Zonyl A which contairns 0,012 g phosphorus is adeO. The temperature of the bath is increased to,2300C. At 4 25 2301C. Q0O384 g dirnethyl ,3'-(1,4-phenylene)bis- (2-cyanopropenoate] are added to the flask. Five minutes after this addition, a vacuum with a slow stream of nitrogen bleeding into the sys'tem is applied over a five-minute period u,,itji the pressure Is reduced to 2,00 mm Hg The flask and contents are heated at Z30 0 C Under a pressure of 200 =m Hg for minutes. The metal bath temperature is increased to 27011C, At 2701C the pressure is reduced slowly to 100 mm Hg. The flask and contents are heated at MfQC under a pressure of 100 mm Hp, for 30 minutes.

26 The metal bath temperature is then increased to 285 0

C

and the pressure is reduced slowly to 4.5 mm Hg. The flask and contents are heated to 285 0 C under pressure of 4.5 mm Hg for 25 minutes and the pressure then reduced to 0.25 mm Hg and polycondensation continued for 40 minutes. The flask is removed from the metal bath and allowed to cool in nitrogen atmosphere while the polymer crysta)!izes. The resulting polymer has an inherent visco. )f 0.54 measured in a 60/40 10 ratio by weight of lol/tetrachloroethane at a concentration of I.L r 100 ml. An amorphous 13-mil thick film molded from this polymer to simulate the sidewall of a container transmits less S" than 10% light from 250 to 370 nm whereas a 13-mil 15 film prepared from a like polyester without the copolymerized absorber transmits greater than light at all wavelengths above 320 nm.

EXAMPLE 82 X-19835-28 The procedure described in Example 81 is o 20 tepeated using 0.0384 g of 3,3'-(i,,4-phenylene)bisfee*:. 2-(4-methoxycarbonyl)phenyl-2-propenenitrile] S. prepared according to the procedure described in Example 2 instead of the bis-methine compound used in Example 81. The resulting polymer has an inherent viscosity of 0.51 measured in a 60/40 ratio by weight of phenol/tetrachloroethane at a concentration of g per 100 mL. An amorphous 15--mil thick film molded from this polyester shows a strong absorption peak with a vaximum at 374 nm.

EXAMPLE 83 X-1956/-55 The procedure described in Example 81 is repeated iusing 0.0384 g of diethyl phenylene)bis-[2-(2-benzoxazolyl)-2-propenoate I ii 27prepared in Example 3 rather than the bis-methine compound used in Example 81. The resulting polymer has an inherent viscosity of 0.53 measured in a 60/40 ratio by weight of phenol/tetrachloroethane at a concentration of 0.5 g per 100 mL. An amorphous 13-mil thick film molded from this polyester exhibits a strong absorption peak with a maximum at 371 nm.

EXAMPLE 84 X-19258-011 The procedure described in Example 81 is 10 repeated using 0.0384 g of diethyl phenylene)bis-[2-benzoyl-2-propenoate] of Example instead of the bis-methine absorber used in Example 81. The resulting polymer has an inherent viscosity of 0.50 measured in a 60/40 ratio by weight of phenol/tetrachloroethane at a concentration of 0.5 g per 100 mL. An amorphous 13-mil thick film molded from this polyester exhibits a strong absorption peak with a maximum at 350 nm.

While the invention has been described in detail 20 with particular reference to preferred em-odiments thereof, it will be understood that variations and modifications can be effected within the spirit and scope of the invention.

Claims (11)

1. A composition comprising molding or fiber grade condensation polymer having copolymerized therein a total of from 1.0 to 10,000 ppm, of the reactant residue moieties of one or a mixture of bis-methine reactants of the formula 1 1 2 M =HC-Ar -CH=M wherein 1 1,4-phenylene radical; and 1 2 M and M are the same or different and each is a disubstituted methylene group having the structure 2 .3 15 3 NC-C or R -08- wherein 4A 3 S" R is -O-R X-R, X-R S X or -AR 2 -R 4 and R 2 is X-R 4 or wherein, 3 R Is hydrogen, allyl or an unsubstituted or substituted alkyl, cycloalkyl or phenyl radical; X is a divalent alkylene, cycloalkylene or phenylene radical or a combination thereof which may contain within the divalent chain one or two atoms or radicals selected from -SO 2 i I i i ill I r I re I fI 1-- 1 29 3 R3 0R 6 or -N-R wherein S S S9 *S 5 V 4 *5 9 5 55 I. V S 4* 55 4r 9 Ir R is an unsubstituted or substituted alkyl, cycloalkyl or phenyl radical; 4 R is a group that is reactive with one of the monomers from which the conidensation polymer is prepared; 2 Ar is an unsubstituted or substituted phenylene or heterocyclic arylene radical; and R is hydrogen, R or -X-R wherein the bis-methine moiety absorbs radiation significantly in the range of 250 to 390 nm and is non-extractable from said polymer and is stable under the conditions the polymer is prepared or processed,

2.Th coThedpo-it--o l-*-i-mI 1 the -total amount of bis-methine moiety present is from about 2.0 to about 1500 ppm.

3. The composition of Claim 1 wherein t total bis-methine moiety present is fro about 100 to about 800 ppm.

4. The composition of Clai 1 wherein the polymer is a linear polyest and the bis-methine compound has the ormula R 3 R. wherein R3 is defined above and R is fa-4r-l i L ILL~-L -29a- 2. A composition as claimed in claim 1 wherein the total amount of bis-methine moiety present is from about to about 1500 ppm. 3, A composition as claimed in claim 1 wherein the total bis-methine moiety present is from about 100 to about 800 ppm. 4. A composition as claimed in any one of claims 1 to 3 wherein the polymer is a linear polyester and the bis-methine compound has the formula R CH=-- 3 *s 3 8 .wherein R is defined above and R is hydrogen, alkyl or "halogen. *0 *S i e e *0 eo A composition as claimed in claim 4 wherein the polymer is poly(ethylene terephthalate) or poly(ethylene terephthalate) modified with up to 5 mole percent of 1,4-cyclohexanedimethanol, R 3 is alkyl of 1 to 6 carbon R8. atoms and Ris hydrogen.

6. A composition as claimed in any one of claims I to 3 wherein the polymer is a linear polyester and the bis-methine compound has the formula Swherein .see 1 R is lower a 1.koxyca rbonylphenyl, lower alkoxycarbonylbenzoyl, lower al1koxyc arbonyl -2 -benzoxazoyl, lower alkoxycarbonyl-2-benzothiazoyl, lower alkoxycarbonyl-2- *.benzimidazolyl, N-lower hydroxyalkylcarbamoyl or N-lower alkanoyloxy-lower-al1kylcarbamoyl; R 8is lower alkyl, halogen or hydrogen; and n is 1 or 2.

7. A composition as claimed in claim 6 wherein the *:polymer is poly(ethylene terephthalate) or poly(ethyliene terephthalate) modified with up to 5 mole percent of .14ccoeaeiehnland Ris hydrogen. 0: 8.A composition as claimed in any one of claims I to '3 wherein the polymer is a linear polyester and the bis-methine %%.:compound has the formula 2 2 *R 3 wherein JR is lower alkyl; R 2 is benzoylA, 2-benzoxazolyl, 2-benzothiazoly1 or 2-benz imidazo lyl; R is lower alkyl, halogen or hydrogeii; and n is 1 or 2, 91 A composition as claimed in claim 8 Wherein the polymer is poly(ethylene terephthalate) or poly(ethylene berephthalate) modified with up to 5 mole percent, 4/ 4-cyclohexanedimethanol and R 8 is hydrogen. i ir:: ll I I 4 -31- A composition as claimed in any one of claims 4, 6 or 8 wherein the polyester is comprised of from about 75 to 100 mol terephhalic acid residue and from about 75 to 100 mol ethylene glycol residue and the polyester contains a total of 100 to 800 ppm of one or a mixture of the bis-methine moieties.

11. A composition as claimed in any one of claims 1 to 3 wherein the polymer is unsaturated polyester having an acid moiety comprised of fumaric or maleic acid or mixtures thereof and up to about 60 mol of one or a mixture of 0-phthalic, iso-phthalic, or terephthalic acids, and having a glycol moiety comprised of one or a mixture of propylene glycol, neopentyl glycol, 2,2,4-trimethyl-l,3-pentanediol, ethylene glycol or diethylene glycol, '12. A composition as claimed in claim 10 wherein the acid moiety is comprised of from about 75 to 100 mol o-phthalic acid and maleic acid in a mole ratio of from about 1/2 to about 2/1, and the glycol moiety is comprised of from about 75 to 100 mol propylene glycol.

13. A composition as claimed in any one of claims 1 to 12 containing a curing amount of an ethylenically unsaturated monomer.

14. A cured, formed article of the composition as claimed in claim 13. A fiber of the composition as claimed in any one of claims 1 to 13 dyed with from about 0.01 to about 5.0% by weight based on weight of fiber of a disperse dye.

16. A formed article of the composition as claimed in any one of claims 1 to 12.

17. A composition as claimed in claim 1 substantially as hereinbefore described, with reference to any one of the examples. DATED: 9 November 1990 P'HILLIPS ORMONDE FITZPATRICK Patent Attorneys for: ^MKO E A STMAN KODAK COMPANY P4S uW/188lU vr Si"9