Claims
- 1. A method for preparing a composition comprising polycyclic polycarbonate or thiol analog oligomers which comprises contacting (A) a composition comprising a mixture of (1) at least one compound having the formula
- R.sup.1 (Y.sup.1 COX.sup.1).sub.2 (VII)
- wherein each R.sup.1 is independently a divalent aliphatic, alicyclic or aromatic radical, each Y.sup.1 is independently oxygen or sulur and X.sub.1 is chlorine or bromine, with (2) at least one compound of the formula
- (HY.sup.1).sub.2 A.sup.1 --Y.sup.2 --A.sup.2 (Y.sup.1 H).sub.2, (VIII)
- wherein each of A.sub.1 and A.sup.2 is a trivalent aromatic radical and Y.sup.2 is a bridging radical in which one or two atoms separate A.sup.1 from A.sup.2 ;
- with or without (3) at least one bis(active hydrogen) compound having the formula
- R.sup.3 (Y.sup.3 H).sub.2, (IX)
- wherein each Y.sup.3 is independently sulfur when the corresponding R.sup.3 is aliphatic or alicyclic and oxygen or sulfur when the corresponding R.sup.3 is aromatic; with
- (B) at least one oleophilic aliphatic or heterocyclic tertiary amine and
- (C) an aqueous alkali metal hydroxide solution having a concentration of about 0.1-10 M;
- said contact being effected under conditions resulting in high dilution of (A), or the equivalent thereof, in a substantially non-polar organic liquid which forms a two-phase system with water, for a period of time sufficient to form said polycyclic oligomers; and recovering said oligomers.
- 2. A method according to claim 1 wherein (A) consists essentially of a mixture of (1) a bischloroformate of formula VII in which Y.sup.1 is oxygen, X.sup.1 is chlorine and R.sup.1 has the formula
- --A.sup.3 --Y.sup.3 --A.sup.4, (III)
- wherein each of A.sup.3 and A.sup.4 is a single-ring divalent aromatic radical and Y.sup.3 is a bridging radical in which one or two atoms separate A.sup.3 from A.sup.4 ; and (2) a tetraphenol of formula VIII in which each Y.sup.1 is oxygen.
- 3. A method according to claim 2 wherein each of A.sub.1 and A.sup.2 is an unsubstituted single-ring aromatic radical and Y.sup.2 is methylene, carbonyl, thio, sulfoxy or sulfone.
- 4. A method according to claim 3 wherein (B) is triethylamine, (C) is sodium hyroxide and the organic liquid is methylene chloride.
- 5. A method according to claim 4 wherein (A-1) is a crude bischloroformate product.
- 6. A method according to claim 5 wherein (A) comprises about 0.5-10.0 mole percent of tetraphenols of the formula ##STR5## wherein R.sup.2 is a C.sub.1-4 primary or secondary alkyl radical.
- 7. A method according to claim 3 wherein each of A.sup.3 and A.sup.4 is p-phenylene and Y.sup.3 is isopropylidene.
Parent Case Info
This application is a division of copending application Ser. No. 913,908, filed Oct. 1, 1986, now U.S. Pat. No. 4,794,160, which is a division of application Ser. No. 801,437, filed Nov. 25, 1985, now abandoned.
This invention relates to new polycyclic oligomeric compositions, methods for their preparation and uses thereof. In particular, it relates to crosslinkable cyclic polycarbonate oligomers.
Polycarbonates are well known polymers which have good property profiles, particularly with respect to impact resistance, electrical properties, optical clarity, dimensional rigidity and the like. These polymers are generally linear, but can be made with branched sites to enhance their properties in specific ways. Low levels of branching are generally incorporated into the resin by copolymerizing into the polymer backbone a polyfunctional reagent to yield a thermoplastic polycarbonate resin with enhanced rheological properties and melt strength which make it particularly suitable for such types of polymer processing procedures as the blow molding of large, hollow containers and the extrusion of complex profile forms. Special manufacturing runs must be set aside to prepare these branched polycarbonate resins.
Sufficiently higher levels of branching sites in the resin will cause resin chains actually to join to each other to form partially or fully crosslinked resin networks which will no longer be thermoplastic in nature and which are expected to exhibit enhancements over corresponding linear resins in physical properties and/or in their resistance to abusive conditions, such as exposure to organic solvents. A wide variety of means have been employed to produce crosslinking in polycarbonate resins. They generally involve the incorporation of a suitably reactive chemical group into the resin chain at its time of manufacture, as an additive to the resin after manufacture, or both. These reactive groups and the reactions they undergo are generally different from those characteristic of polycarbonate resins themselves and therefore tend to have detrimental side effects on the physical and/or chemical properties of the polymer. The conventional test used to judge the success of these means for crosslinking is to observe the formation of gels due to the crosslinked material when a resin sample is mixed with a solvent, such as methylene chloride, in which normal linear polycarbonate resin is highly soluble.
A principal object of the present invention, therefore, is to provide useful new compositions of matter, and methods for their preparation and use.
A further object is to provide compositions which form crosslinked polycarbonates, and precursors therefor.
A still further object is to provide new polycarbonate compositions with advantageous properties.
Other objects will in part be obvious and will in part appear hereinafter.
In one of its aspects, the present invention includes compositions comprising polycyclic oligomers having structural units of both of the formulas ##STR1## wherein:
each R.sup.1 is independently a divalent aliphatic, alicyclic or aromatic radical;
each of A.sup.1 and A.sup.2 is a trivalent aromatic radical;
each Y.sup.1 is independently oxygen or sulfur; and
Y.sup.2 is a bridging radical in which one or two atoms separate A.sup.1 from A.sup.2.
Before proceeding with a detailed discussion of the invention, it may be useful to explain some terms used herein. The term "thiol analog", when used with reference to dihydroxy compounds, oligomers and polycarbonates, includes monothio and dithio compounds in which the carbonsulfur bonds are single bonds only. The terms "resin" and "resinous composition" include polycarbonates and polymers containing thiol analogs of the carbonates.
As will be apparent from the above, the polycyclic oligomers of this invention may contain organic carbonate, thiolcarbonate and/or dithiolcarbonate units. The various R.sub.1 values in formula I may be different but are usually the same, and may be aliphatic, alicyclic, aromatic or mixed; those which are aliphatic or alicyclic generally contain up to about 8 carbon atoms. Suitable R values include ethylene, propylene, trimethylene, tetramethylene, hexamethylene, dodecamethylene, 1,4-(2-butenylene), 1,10-(2-ethyldecylene), 1,3-cyclopentylene, 1,3-cyclohexylene, 1,4-cyclohexylene, m-phenylene, p-phenylene, 4,4'-biphenylene, 2,2-bis(4-phenylene)propane, benzene-1,4-dimethylene (which is a vinylog of the ethylene radical and has similar properties) and similar radicals such as those which correspond to the dihydroxy compounds disclosed by name or formula (generic or specific) in U.S. Pat. No. 4,217,438, the disclosure of which is incorporated by reference herein. Also included are radicals containing non-hydrocarbon moieties. These may be substituents such as chloro, nitro, alkoxy and the like, and also linking radicals such as thio, sulfoxy, sulfone, ester, amide, ether and carbonyl. Most often, however, all R.sup.1 radicals are hydrocarbon radicals.
Preferably at least about 60% and more preferably at least about 80% of the total number of R.sup.1 values in the polycyclic oligomers, and most desirably all of said R.sup.1 values, are aromatic. The aromatic R.sup.1 radicals preferably have the formula
In formula III, the A.sup.3 and A.sup.4 values may be unsubstituted phenylene or substituted derivatives thereof, illustrative substituents (one or more) being alkyl, alkenyl (e.g., crosslinkable-graftable moieties such as vinyl and allyl), halo (especially chloro and/or bromo), nitro, alkoxy and the like. Unsubstituted phenylene radicals are preferred. Both A.sup.3 and A.sup.4 are preferably p-phenylene, although both may be o- or m-phenylene or one o- or m-phenylene and the other p-phenylene.
The bridging radical, Y.sup.3, is one in which one or two atoms, preferably one, separate A.sup.3 from A.sup.4. It is most often a hydrocarbon radical and particularly a saturated radical such as methylene, cyclohexylmethylene, neopentylidene, 2-[2.2.1]bicycloheptylmethylene, ethylene, ethylidene, isopropylidene, cyclohexylidene, cyclopentadecylidene, cyclododecylidene or adamantylidene, especially an alkylidene radical. Also included, however, are unsaturated radicals and radicals which are entirely or partially composed of atoms other than carbon and hydrogen. Examples of such radicals are 2,2-dichloroethylidene, carbonyl, thio and sulfone. For reasons of availability and particular suitability for the purposes of this invention, the preferred radical of formula III is the 2,2-bis(4-phenylene)propane radical, which is derived from bisphenol A and in which Y.sup.3 is isopropylidene and A.sup.3 and A.sup.4 are each p-phenylene.
As noted, each Y.sup.1 value is independently oxygen or sulfur. Most often, all Y.sup.1 values are oxygen and the corresponding compositions are cyclic polycarbonate oligomer mixtures.
An essential feature of the compositions of this invention is the presence therein of structural units having formula II, which lead to an overall polycyclic structure. The number of rings in any individual molecule of said compositions will depend on the proportions of reactants and the reaction conditions. The following molecular structures are illustrative. ##STR2## wherein m and n are integers, typically from 1 to about 11.
In formula II, each Y.sup.1 value may be oxygen or sulfur and all Y.sup.1 values are usually oxygen. The Y.sup.2 values are bridging radicals similar to those defined hereinabove for Y.sup.3, and are usually methylene, carbonyl, thiol, sulfoxy or sulfone. The A.sup.1 and A.sup.2 values are usually trivalent single-ring aromatic radicals; they are preferably unsubstituted but may contain substituents such as those previously identified with respect to A.sup.3 and A.sup.4.
The structural units of formula II may be considered as being derived from the corresponding tetraphenols and their thiol analogs. Illustrative tetraphenols are bis(2,4-dihydroxy-3-methylphenyl)methane, 2,2',4,4'-tetrahydroxybiphenyl, 2,2',4,4'-tetrahydroxybenzophenone, bis(2,4-dihydroxyphenyl) sulfide, bis(2,4-dihydroxyphenyl) sulfoxide and bis(2,5-dihydroxyphenyl) sulfone.
Certain of these tetraphenols, particularly the bis(2,4-dihydroxy-3-alkylphenyl)methanes, are novel compounds. Therefore, another aspect of the invention is tetraphenols having the formula ##STR3## wherein R.sup.2 is a C.sub.1-4 primary or secondary alkyl radical and especially methyl.
Such tetraphenols may be prepared by reacting a 2-alkylresorcinol with formaldehyde under acidic conditions, typically in aqueous solution and at a temperature in the range of 10.degree.-50.degree. C. Most often, approximately equimolar amounts of 2-alkylresorcinol and acid are present and the molar ratio of 2-alkylresorcinol to formaldehyde is about 3-6:1. The following example is illustrative. All parts are by weight.
US Referenced Citations (1)
| Number |
Name |
Date |
Kind |
| 4794160 |
Shannon et al. |
Dec 1988 |
|
Divisions (2)
|
Number |
Date |
Country |
| Parent |
913908 |
Oct 1986 |
|
| Parent |
801437 |
Nov 1985 |
|
Patent Grant
4888411
