Halovinylidene arylene polymers are prepared from the dihydrohalogenation of the polymeric reaction product of an aromatic compound containing nuclearly-bonded hydrogen and either chloral or bromal, in the presence of a strong acidic catalyst.
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1. A polymer composed of recurring units of the formula ##STR20## where R and R' are members selected from the class consisting of hydrogen, halogen, and the methyl radical, Z is a direct bond or is a member selected from the class consisting of --O--, --S--, the
O--(CH2)n O]q --O--(CH2)2 O]q radical, and divalent radicals of the general formula ##STR21## where Y is chlorine or bromine, Q is a member of the class of --O--, --S--, --SO2 --, >C=O and divalent alkyl radicals of from 1 to 4 carbon atoms, m is a whole number in excess of 1, and n and q are whole numbers from 1 to 2, inclusive q is a whole number equal to 1 or 2. 2. A polymer as in
3. A polymer as in
4. A polymer as in
5. A polymer as in
6. The process for making polymers polymer composed of recurring structural units of the formula ##STR26## which process comprises dehydrohalogenating a precursor polymer composed of recurring structural units of the formula ##STR27## in the presence of a dehydrohalogenating system composed of a tertiary organic amine and an inorganic base, where R and R' are members selected from the class consisting of hydrogen, halogen and the methyl radical, Z is a direct bond or is a member selected from the class consisting of --O--, --S--, divalent alkyl hydrocarbon radicals of from 1 to 4 carbon atoms, the
--O--(CH2)n O]q --O--(CH2)2 O]q radical, and divalent radicals of the general formula ##STR28## where Y is chlorine or bromine, Q is a member of the class of --O--, --S--, --SO2 --, >C=O and divalent alkyl radicals of from 1 to 4 carbon atoms, and m is a whole number in excess of 1 . and q is a whole number equal to 1 or 2. 7. The process of
8. The process as in
9. The process as in
10. The process as in
11. The process as in
12. The process as in
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This invention is concerned with halovinylidene arylene polymers and methods for making the same. More particularly, the invention relates to a polymeric composition composed of recurring structural units of the formula ##STR1## where R and R' are members selected from the class consisting of hydrogen, halogen (e.g., chlorine, bromine, fluorine, etc.) and the methyl radical, Z is a direct bond or is a member selected from the class consisting of --O--, --S--, divalent alkyl hydrocarbon radicals of from 1 to 4 carbon atoms, the
thataddition additional funnel over a period of one-half hour. Diphenyl ether in an amount equal to 21.48 grams (0.13 mol) and 60 ml 1,1,2,2-tetrachloroethane were added and the solution heated at 70°C for about 21/2 hours. After cooling to room temperature, additional TFAA (20 grams, 0.095 mol) was added dropwise over a period of 0.5 hours. BF3 gas was then bubbled into the solution at the rate of one bubble per second for one hour and the solution heated at 70°C for about 8 hours. The addition of BF3 at room temperature was repeated four times with subsequent heating of the solution for 8, 7, 7, and 16 hours, respectively. The solution was cooled to room temperature, diluted with 200 ml chloroform, and 2000 ml methanol was added to precipitate the polymer. The precipitated polymer was removed by filtration, washed with methanol and dried in vacuum at 50°C to yield a colorless polymer composed of recurring units of the formula ##STR17## where m is a whole number greater than 1. The elemental analyses on the polymer were as follows:
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| Percent Found Theoretical |
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| C 56.3 55.13 |
| H 2.95 3.03 |
| Cl 35.03 35.49 |
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About 4.8 grams of a diphenylether-chloral polymer having an intrinsic viscosity of 0.27 dl/g prepared similarly as in Example 7 was dissolved in 30 ml pyridine and the solution was heated to reflux temperature to the mass for 24 hours. The reaction mixture was cooled and poured into a large quantity of water. The polymer which precipitated was isolated, soaked in hot water four times and then washed with methanol. The polymer thus obtained was dried under vacuum at 50° C to give about 3.8 grams (about a 90.5% yield) of a dichlorovinylidene polymer composed of recurring structural units of the formula ##STR18## where m is a whole number in excess of 1. This polymer had an intrinsic viscosity in chlorobenzene of 0.030 dl/g.
The following Table I shows the improvements in the thermal stability attained by the dehydrohalogenation reaction. It will also be noted that the glass transition temperature (Tg) was lowered by a few degrees.
| TABLE I |
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| Polymer of TD (° C)1 |
| Tg2 |
| Example No. Air N2 ° C |
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| 2 378 378 101 |
| (311)3 |
| (311) (116) |
| 4 370 385 99 |
| (290) (305) (117) |
| 5 382 390 111 |
| (295) (305) (126) |
| 8 455 472 169 |
| (318) (318) (212) |
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| 1 Temperature at which 5% weight loss occurred at heating rate of |
| 10° C/minute. |
| 2 Determined by differential scanning calorimetry. |
| 3 Numbers in parentheses are those of precursor polymers. |
When an attempt was made to ignite the above-mentioned four polymers, it was found that they were flame resistant and even when ignited, they were self-extinguishing. Instead of exhibiting any drip, the polymers formed stable chars while burning. The oxygen indices of the polymers of Example 2 and 8 were 29.2 and 56.0, respectively, exceptionally high members. The polymer of Example 8 was additionally treated and found that it had outstanding non-smoke properties, under the National Bureau of Standard tests, this polymer showed a minimum light transmission (through smoke) of 73%, indicating one of the lowest maximum smoke density values encountered.
Mechanical tests were conducted on the polymer of Examples 2 and 8 based on compression molded samples. The results of these tests are as follows:
| TABLE II |
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| Polymer of Polymer of |
| Example 2 Example 8 |
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| Flexural Modulus |
| 4.9 × 105 psi |
| 4.26 × 105 psi |
| Flexural Strength |
| 16.9 × 103 psi |
| 18.1 × 103 psi |
| Notched Izod Impact |
| 0.50 ft. lb. |
| Strength |
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About 0.888 grams of a diphenylether-chloral polymer as in Example 7 was dissolved in 20 ml toluene, together with 5 grams anhydrous potassium carbonate and 0.05 ml of DBN. The mixture was stirred and heated at the reflux temperature of the mass for about one hour. The reaction mixture was then filtered and the inorganic precipitate was washed with toluene and the combined filtrate and the wash water were added to methanol. The white polymer which precipitated was collected by filtration, dried under vacuum to give 0.75 gram (96.4% yield) of a polymer composed of recurring structural units of formula XIV.
It has also been found that 18-membered cyclic ethers containing nitrogen atoms have specific complexing ability toward alkali metal ions, notably sodium and potassium, making them useful as catalysts for the dehydrohalogenation of the aforementioned polymers of formula III. The complex of the aforesaid cyclic ether with the metallic ions solubilizes salts of such ions and dissociates well in non-polar organic solvents. In addition to such cyclic ether amines enhancing the rate of dehydrohalogenation, they can be readily recovered from reaction mixtures in close to quantitative yield thus contributing to the economic aspects of any process using such cyclic ethers. Such nitrogen-containing cyclic ethers may be designated by the general formula ##STR19## where R is a monovalent saturated aliphatic hydrocarbon of from 1 to 6 carbon atoms, for example, methyl, ethyl, propyl, butyl, isobutyl, cyclohexyl, etc.
The following example shows a means for preparing such a cyclic ether.
14.70 grams (0.0477 mol) 1,2-bis(2-n-butylaminoethoxy)benzene [obtained from the reaction of 1,2-bis(2-chloroethoxy)benzene and n-butylamine] and 11.21 grams (0.0477 mol) 1,2-bis(2-chloroethoxy)benzene were dissolved in 120 ml of N-methylpyrrolidone. The solution was heated under nitrogen at 120-125°C for 1 hour and then 5 grams anhydrous sodium carbonate was added and the solution was further heated at 120-125°C for 16 hours. Three portions of sodium carbonate (3 grams each) were then added at one hour intervals for a total heating time of 20 hours. The solvent was removed under vacuum, and the residue dissolved in toluene and the solution washed with water. The toluene solution was evaporated to leave a semi-solid which was triturated with ethanol. The crystalline precipitate which was obtained was filtered and recrystallized from cyclohexane to give the crown ether of formula XV where R is n-butyl in an amount equal to 8.19 grams (36.7% yield). The melting point of this product was 151-152°C The structure of this crown ether compound was established by the analyses for the elements which were as follows:
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| Percent Found Calculated |
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| C 71.1 71.5 |
| H 8.8 9.00 |
| N 6.0 5.95 |
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Using 0.5 gram of the amino crown ether of Example 10, 75.45 grams of the diphenylether-chloral polymer of Example 7 was dissolved in 250 ml toluene together with 40.5 grams of a 50% aqueous solution of sodium hydroxide, 0.5 gram phenol and 27 grams sodium hydroxide pellets. The mixture was stirred under a nitrogen atmosphere and heated at the reflux temperature of the mass to 108°C for about 150 minutes. The solution was cooled, the organic layer was separated, washed with 0.1 N hydrochloric acid. The organic layer was poured into methanol and stirred causing the polymer to precipitate. The latter polymer was filtered, washed with methanol and dried to give 65.31 grams (98.4% yield) of the dehydrochlorinated polymer composed of recurring structural units of formula XIV. The aqueous acid extract was washed with toluene, and made basic with sodium hydroxide. The basic solution was extracted with chloroform using two quantities of 50 ml each time, the chloroform solution was washed with water and evaporated to dryness. The white crystals of the initial crown amino ether was obtained as the residue in a yield of about 0.048 gram (80.4% yield), indicating the ease with which the amino crown ether can be recovered.
The compositions of the present invention have application in a wide variety of physical shapes and form, including the use as of films, molding compounds, coatings, etc. When used as films or when made into molded products, these polymers, including laminated products prepared therefrom, possess good physical properties. Films formed from the polymeric compositions of this invention may be used in applications where films have been used previously. Thus, the compositions of the present invention can be used in automobile applications for decorative and protective purposes, as dielectric capacitors, as coil and cable wrappings (form wound coil insulation for motors), for containers and container linings; in laminating structures where films of the present composition or where solutions of the claimed compositions of matter are applied to various heat-resistant or other type of materials such as asbestos, mica, glass fiber and the like and superposing the sheets one upon the other and pressures to effect flow and cure of the resinous binder to yield cohesive laminated structures. Films made from these compositions of matter can also serve in printed circuit applications.
Alternatively, solutions of the compositions herein described can be coated on electrical conductors such as copper, aluminum, etc., and thereafter the coated conductor can be heated at elevated temperatures to remove the solvent. If desired, an additional overcoat may be applied to such insulated conductors including the use of polymeric coatings, such as polyamides, polyesters, silicones, polyvinylformal resins, epoxy resins, polyimides, polytetrafluoro-ethylene, etc. The use of the compositions of the present invention as overcoats on other types of insulation is not precluded.
Applications which recommend these polymers (which advantageously have an intrinsic viscosity [η] of at least 0.15 dl/g when measured in CHCl3) include their use as binders for asbestos fibers, carbon fibers, and other fibrous materials in making brakelinings. In addition, molding compositions and molded articles may be formed from the polymeric compositions in this invention by incorporating such fillers as asbestos, glass fibers, talc, quartz, powder, wood flour, finely divided carbon, silica, into such compositions prior to molding. Shaped articles are formed under heat, or under heat and pressure in accordance with practices well known in the art. In addition, various pigments and dyes may be incorporated as well as various types of inhibitors depending on the application intended.
The compositions herein defined may suitably be incorporated in other materials to modify the properties of the latter or in turn their properties may be modified by the incorporation of the other material. For example, they may be compounded with substances such as natural or synthetic rubbers; synthetic resins such as epoxy resins, phenolaldehyde resins, urea-aldehyde resins, alkyd resins, etc.; cellulostic material such as paper, inorganic and organic esters of cellulose such as cellulose acetate; cellulose ether, such as methyl cellulose, ethyl cellulose, benzyl cellulose, etc. In some instances, plasticizers and other modifying agents may be used in combination with the claimed polymers. These polymers including low molecular weight products, are useful themselves or as additives to other polymers of producing products having low flammability.
It will, of course, be apparent to those skilled in the art that in addition to the dichlorovinylidene arylene compositions specifically referred to in the foregoing examples, other polymers including dibromovinylidene arylene polymers, solvents, catalysts, etc., many examples of which have been described above, may be employed without departing from the scope of the invention. The processing techniques may be varied widely employing the many conditions recited previously.
| Patent | Priority | Assignee | Title |
| 4254252, | Nov 08 1976 | General Electric Company | Cyclic polyformals and method for making |
| Patent | Priority | Assignee | Title |
| 3391116, | |||
| 3824214, |
| Executed on | Assignor | Assignee | Conveyance | Frame | Reel | Doc |
| Mar 18 1977 | General Electric Company | (assignment on the face of the patent) | / | |||
| Mar 07 2008 | SABIC INNOVATIVE PLASTICS IP B V | CITIBANK, N A , AS COLLATERAL AGENT | SECURITY AGREEMENT | 021423 | /0001 |
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