CA1117247A - Film forming, moldable aromatic polyformal resins and method for making same - Google Patents
Film forming, moldable aromatic polyformal resins and method for making sameInfo
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- CA1117247A CA1117247A CA000289785A CA289785A CA1117247A CA 1117247 A CA1117247 A CA 1117247A CA 000289785 A CA000289785 A CA 000289785A CA 289785 A CA289785 A CA 289785A CA 1117247 A CA1117247 A CA 1117247A
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- Prior art keywords
- reaction mixture
- bisphenol
- accordance
- polyformal
- methylene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4006—(I) or (II) containing elements other than carbon, oxygen, hydrogen or halogen as leaving group (X)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/46—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen
- C08G2650/48—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen containing fluorine, e.g. perfluropolyethers
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
FILM FORMING, MOLDABLE AROMATIC
POLYFORMAL RESINS AND METHOD FOR MAKING SAME
Abstract of the Disclosure The present invention relates to polyformal resins having an intrinsic viscosity of at least 0.3 in chloroform at 25°C and a method for making such materials. The polyformal resins of the present invention are high molecular weight thermo-plastic film forming injection moldable resins. In preparing the polyformal resins, a bisphenol is reacted with an excess of a methylene halide under substantially anhydrous conditions in the presence of an excess of alkali hydroxide.
POLYFORMAL RESINS AND METHOD FOR MAKING SAME
Abstract of the Disclosure The present invention relates to polyformal resins having an intrinsic viscosity of at least 0.3 in chloroform at 25°C and a method for making such materials. The polyformal resins of the present invention are high molecular weight thermo-plastic film forming injection moldable resins. In preparing the polyformal resins, a bisphenol is reacted with an excess of a methylene halide under substantially anhydrous conditions in the presence of an excess of alkali hydroxide.
Description
The present invention relates to film forminy poly-formal resins having an intrinsic viscosity of at least 0.3 dl/g. More particularly, the present invention relates to the reaction of methylene halide and bisphenol is a mixture having an excess of methylene halide and alkali hydroxide.
Prior to the present invention, as shown by Barclay U.S. Patent 3,069,386 dated December 18, 1962, polyformal `
resins were prepared by reacting a disodium diphenolate and a methylene halide in the presence of a polar organic solvent under substantially anhydrous conditions. As taught by Barclay, the reaction was sensitive to small amounts of water and other impurities containing hydrxyl groups which caused undesirable side reactions. As a result, the poly-formal resins made by the method of Barclay had an extremely .
low reduced viscosity. It was found that the polyformal was unsuitable as a thermoplastic because it was extremely brittle and has very little strength. As a result, Barclay used the polyformal as an intermediate for making a ~ :
polycarbonate-polyformal copolymer by a standard phosgenation procedure.
The present invention is based on the discovery that film forming polyformals having an intrinsic viscosity as .
high as 2.0 dl/g in chloroform at 25C and consisting -~
essentially of chemically combined units of the formula, (1) -OROCH2- , where R is a divalent C(6_30) aromatic radical, can be made by effecting a reaction under substantially anhydrous con-ditions between methylene halide and a bisphenol of the formula, 7 ~
Prior to the present invention, as shown by Barclay U.S. Patent 3,069,386 dated December 18, 1962, polyformal `
resins were prepared by reacting a disodium diphenolate and a methylene halide in the presence of a polar organic solvent under substantially anhydrous conditions. As taught by Barclay, the reaction was sensitive to small amounts of water and other impurities containing hydrxyl groups which caused undesirable side reactions. As a result, the poly-formal resins made by the method of Barclay had an extremely .
low reduced viscosity. It was found that the polyformal was unsuitable as a thermoplastic because it was extremely brittle and has very little strength. As a result, Barclay used the polyformal as an intermediate for making a ~ :
polycarbonate-polyformal copolymer by a standard phosgenation procedure.
The present invention is based on the discovery that film forming polyformals having an intrinsic viscosity as .
high as 2.0 dl/g in chloroform at 25C and consisting -~
essentially of chemically combined units of the formula, (1) -OROCH2- , where R is a divalent C(6_30) aromatic radical, can be made by effecting a reaction under substantially anhydrous con-ditions between methylene halide and a bisphenol of the formula, 7 ~
(2) H0-R-OH
where R is defined above, in the presence of an alkali hydroxide, an~ the alkali hydroxide and methylene halide are maintalned during the intercondensation reaction at greater than stoichio-metric concentrations. Unlike Barclay's polyformals, havingintrinsic viscosities less than 0.2 dl/g and undesirable physical properties, such as brittleness, ~he polyformals of the present invention have been found to possess intrinsic viscosities greater than 0.3 and even as high as about 2.0 dl/g. Polyformals derived from bisphenol-A, for example, can have tensile strengths o about 7000 psi with 110% elongation and Gardner impac~ values greater than 320 in. lbs. In addition, the polyormals of the present invention can be converted to copolymers by standard phosgenation techniques and can be blended with various thermo-plastic materials to impart improved properties thereto.
Radicals included by R of formulas 1 and 2 are, orexample, phenylene, tolylene, xylylene, naphthalene, etc.;
halogenated derivatives of such divalent aromatic hydrocarbon radicals, such as chlorophenylene, bromotolylene, etc., divalent radicals, such as -RQR- , O O
where Q can be cyclohexyl, fluorenyl, -0-, -S-, -C-, -S-, -C-, Cl~ ~Cl and -CyH2y~ and y is equal to 1 to 5 inclusive.
There is provided by the present invention a method for making aromatic polyformal resin consisting essentially of chemically combined units of ~ormula (1), where prior to the present invention aromatic polyformals were made by reacting an alkali diphenolate and a methylene halide in the presence of a polar organic solvent under substantially anhydrous con-2~7 ditions resulting in a reaction mixture highly sensitive -to water and other impurities containing hydroxy groups, tending to cause undesirable side reactions and producing polyformals having an intrinsic viscosity of less than 0.2 dl/g, the improvement which comprises agitating under substantially anhydrous conditions a reaction mixture comprising methylene halide, bisphenol of formula (2), alkali hydroxide and a member selected from the class consisting of a phase transfer catalyst and a dipolar aprotic solvent, where there is utilized in the reaction mixture per mole of bisphenol more than 1 mole of methylene halide and more than 2 moles of alkali hydroxide resulting in a reaction mixture less sensitive to water and other impurities containing hydroxy groups, and capable of providing film-forming moldable aromatic polyformals having an intrinsic viscosity greater than 0.3 dl/g.
Some of the bisphenols of formula (2) are compounds such as:
2,2-bis(4-hydroxyphenyl)propane (bisphenol-A);
2,4'-dihydroxydiphenylmethane;
bis-(2-hydroxyphenyl)methane;
1,1-bis-(4-hydroxyphenyl)ethane;
1,1-bis-(4-hydroxyphenyl)propane;
2,2-bis-(4-hydroxyphenyl)-pentane;
where R is defined above, in the presence of an alkali hydroxide, an~ the alkali hydroxide and methylene halide are maintalned during the intercondensation reaction at greater than stoichio-metric concentrations. Unlike Barclay's polyformals, havingintrinsic viscosities less than 0.2 dl/g and undesirable physical properties, such as brittleness, ~he polyformals of the present invention have been found to possess intrinsic viscosities greater than 0.3 and even as high as about 2.0 dl/g. Polyformals derived from bisphenol-A, for example, can have tensile strengths o about 7000 psi with 110% elongation and Gardner impac~ values greater than 320 in. lbs. In addition, the polyormals of the present invention can be converted to copolymers by standard phosgenation techniques and can be blended with various thermo-plastic materials to impart improved properties thereto.
Radicals included by R of formulas 1 and 2 are, orexample, phenylene, tolylene, xylylene, naphthalene, etc.;
halogenated derivatives of such divalent aromatic hydrocarbon radicals, such as chlorophenylene, bromotolylene, etc., divalent radicals, such as -RQR- , O O
where Q can be cyclohexyl, fluorenyl, -0-, -S-, -C-, -S-, -C-, Cl~ ~Cl and -CyH2y~ and y is equal to 1 to 5 inclusive.
There is provided by the present invention a method for making aromatic polyformal resin consisting essentially of chemically combined units of ~ormula (1), where prior to the present invention aromatic polyformals were made by reacting an alkali diphenolate and a methylene halide in the presence of a polar organic solvent under substantially anhydrous con-2~7 ditions resulting in a reaction mixture highly sensitive -to water and other impurities containing hydroxy groups, tending to cause undesirable side reactions and producing polyformals having an intrinsic viscosity of less than 0.2 dl/g, the improvement which comprises agitating under substantially anhydrous conditions a reaction mixture comprising methylene halide, bisphenol of formula (2), alkali hydroxide and a member selected from the class consisting of a phase transfer catalyst and a dipolar aprotic solvent, where there is utilized in the reaction mixture per mole of bisphenol more than 1 mole of methylene halide and more than 2 moles of alkali hydroxide resulting in a reaction mixture less sensitive to water and other impurities containing hydroxy groups, and capable of providing film-forming moldable aromatic polyformals having an intrinsic viscosity greater than 0.3 dl/g.
Some of the bisphenols of formula (2) are compounds such as:
2,2-bis(4-hydroxyphenyl)propane (bisphenol-A);
2,4'-dihydroxydiphenylmethane;
bis-(2-hydroxyphenyl)methane;
1,1-bis-(4-hydroxyphenyl)ethane;
1,1-bis-(4-hydroxyphenyl)propane;
2,2-bis-(4-hydroxyphenyl)-pentane;
3,3-bis-(4-hydroxyphenyl)pentane;
4,4'~dihydroxybiphenyl;
4,4'-dihydroxy-3,3',5,5'-tetramethylbiphenyl; ~:
2,4'-dihydroxybenzophenone;
4,4'-dihydroxydiphenylsulfone;
2,4'-dihydroxydiphenylsulfone;
4,4'-dihydroxydiphenyl sulfoxide;
4,4'-d-~h~droxydiphenyl sulfide;
hydroquinone;
resorcinol;
9,9-bis(4-hydroxyphenyl)-fluorene 3,4'-dihydroxydiphenylmethane;
4,4'-dihydroxybenzophenone;
4,4'-dihydroxydiphenylether;
1,1-dichloro-2,2~bis(4-hydroxyphenyl)ethylene, and 1,1,1-trichloro-2,2-bis(4-hydroxyphenyl)ethane.
Methylene halides which can be used in the practice of the invention, are, for example, methylene chloride, methylene bromide, chlorobromo methane, etc. Alkali hydroxldes which can be employed in the practice of the invention are, for example, potassium hydroxide whi~h can be in the form of pellets, powder, etc., sodium hydroxide, etc.
The polyformal resins having units of ormula (1~ are :~
thermoplastic injection moldable materials which can be con-verted to films and fibers. Preferably, the poly~ormal resins are transparent injection moldable film forming and fiber form~
ing thermoplastic materials. In particular instances, the poly-formal resins of the present invention may bP translucent or cloudy materials, depending on the degree o crystallization of the resulting polymer.
The polyformal resins of the present invention also can be phosgenated to produce polyformal~polycarbonate copolymers.
The polyformals of formula (13 and the polyformal-polycarbonate copolymers can be further blended with other thermoplastic organic resins, such as Lexan ~ resin, PPO ~D resin, Valox ~
resin, all products of the General Electric Company, over wide proportions by weight, such as from 1% ~o 99% of the polyformal resin to 9g% to 1% of the high perfo~mance thermoplastic organic resin. The polyformal reslns of the present invention also can be blended with various fillers, such as glass fiber, silicon carbide whiskers, silica fillers, etc., stabilizers, pigments t flame retardants , etc.
In the practice of the inventi.on, the polyformal resin can be made by effecting contact at a temperature of 0C
to 100C and preferably 40C to 100C between methylene halide and blspheno' in the presence of alksli hydroxide. Reaction can be conducted between excess methylene halide and blsph~nol until the latter has been completely reacted.
Reaction between the methylene halide and the bisphenol can be effected under substantially anhydrous conditions.
Reflux temperatures at atmospheric pressure or above atmospheri.c pressure can be used along with agitation of the mixture. Re2c-tion between methylene halide and bisphenol in the presene of excess alkali hydroxide can be accel~rated by using a substan-tially inert organic solvent in combination with methylene halide, such as a nonpolar or dipolar aprotic organic solvent. Nonpolar organic solvents which can be employed in the methylene halide are, for example, chlorobenzene, dichlorobenzene, benzenQ, toiuene, etc. In addition, there can be used dipolar aprot:ic solvents, such as N-methylpyrrolidone, tetrahydrofuran, dimethylsulfoxide, etc.
Experience has shown that when methylene halide is employed in the absence of a dipolar aprotic solvent, effec~ive results are achieved if a phase transfer catalyst is used to facilitate in situ formation of the alkali salt of the bisphenol and the subsequent condensation reaction with the methylene halide. Suitable phase transfer catalysts are, for examPle, 3.~ 4~7 R~-8971 quaternary ammonium and phosphonlum salts, such as describ~d in JACS 93, 195 (1971) by C.M. Starks. A proportion o~ from about 0.01 to 0.5 mols of the phase transfer catalyst pe.r mol of the bls phenol has been found to provide for effective results, and preferably from 0.02 to 0.10 mols of phase transfer catalyst per mol o bisphenol can be employed.
The intercondensation reaction can be conduc~ed over a period of from 0.1 hours to 24 hours cr greater depetld^ing upor such factors as the nature of the methylene halide, whether an organic solvent is employed in combination with the methylel~e halide,the type of such organi.c solvent, temperature of the reao~
tion, the degree o~ agitation, etc. In particular instances, for example, the more hignly reactive methylene bromide carL b~
substituted for methylene chloride or a mi~ture OL Ctll.OrO~enZen?, with methylene chloride will reflux at a higher temperature. '.
In addition, the reaction can be conducted at elevated pressu-res, or in a closed system to permit the methylene halide ~o xeact with the bisphenol at a higher temperature. Those skilled :in the art would know, for example, that the methylen.e halide itself, when used in excess amo~nts, can serve as a suitab`le organic solven~ as well as a reactant.
The foll.owing examples are given by way of :illustr~
tion and not by way of limitation. All parts are by w~i~ht, unless otherwise speceified.
Example 1.
A mixture of 114 parts ~a. 5 mol) of bisphenol-A, 95 parts (1.7 mol) KOH pellets, 23.3 parts (.05 mol) of ~`~ Aliquat 336 (95% ac~ive monomethyltrlcaprylyl ammonium chloride), a phase transfer catalys~ of the General Mi.lls Co~pany, and 1,009 par~s of methylene chloride was refluxed and s~irred ~-8971 for a period of 21 hours under a nitrogen atmosphere. Wate-r was then added to the mixture and the organic phase was separ-ated and washed with water. A 70% yield of polymer was obtained by adding the organic layer to methanol and filterin~ and dry-ing the resulting precipitate at 60C. ThP polymer was found tohave a Tg of 85C and an intrinsic viscosity o 0.60 dl~g in chloroform at 25C. The polymer was compression molded at 160C
to produce a tough colorless, f~exible transparent film. It also can be cast from chloroform. Eased on elemental anal~sis and ~MR spectrum, the pol~mer was a poly~ormal having t~e formllla ~ Q ~ C ~ CH2~-where n has an average value of 65.
The polyformal had the following p~ysical propert.ies:
Tensile strength, p.s.i. at yield 7-8000 Tensile strength, p. 5. i. at break 7100-7S00 Elongation % 110 Density g/cm3 1.10 Flexural strength p.s.i. 14,3~0 Flexural modulus 105 p.s.i. 73F 4 1 Gardner impac~ stre~gth ~320 in. lb.
Example 2.
A mixture o dimethylsulfoxide, me-thyl~ne chloride, potassium hydroxide, bisphenol-A, and Ali~ at ~7as stirred at a temperature of 60C for 4 hours under substantially anhydrous conditions. The mixture had a weight percent solids oE ~2~/~ and a ratio of aboutllOparts of dimethyl sulfoxide per 90 par~s of methylene chloride. In addition, there was utilized in the mixture a ratio of 2.6 mols of potassium hydroxide per mol of ~ Y24~ RD-8g71 the bisphenol-A while the Aliquat was employed in a proportion of about 0.1 mol of Aliquat per mol of the bisphenol-A. There was obtained a polyformal having an intrinsic Yiscosiky o~
0.548 dl/g in chloroform at 25C. Based on method o~ prepara tion, the polymer consisted essenti.ally of chemically combined blsphenol-A units and formaldehyde units. A tough flexible film was obtained by compression molding, following the ~rocedure of ~
~:xam~le 1, or by casting from a chloroform solution. ~.
Example 3.
A mixture of chlorobenzene, rnethylene chloride, potas-sium hydroxide pellets, bisphenol-A, tetrabutylammonium bromlde and 1.9% by weight of water was stirred at 75C or a period of about 40 minutes. The mixture had a 19% solids content by weight, where the chlorobenzene was utilized in a proportion o:E
about 3 parts o~ chlorobenzene per part of methylene chloride 9 while there was employed about 2.6 mols of potassium hydroxide per mol cf bisphenol-A. In addition, the tetrabutyla~mvnium bromide was present in the mixture in a proportion of ,~bout 0.1 mol of the phase transfer catalyst per mol of bisphenol-A.
There was obtained a 36% yield of polyformal from the above mixture having an intrinsic viscosity of 0.519 dl/g in chloroform at 25C and consisting essentially of chemically combined bisphenol-A units and formaldehyde units. A ~ough flexible film was obtained by casting or compression molding the ~lymer following the procedure previo~sly described. `:
Example 4.
A mixture of N-methylpyrrolidone, methylene chloride, potassium hydroxide pellets and bisphenol-A was stirred for 39 minutes at 70C under substan~ially anhydrous conditions. The N-methylpyrrolidone and the methylene chloride was used in abou~
equal proportions by weight in the polymerization ~ixture having ,. ,,... ....... .. , , ...... ,,,, ~ . . .. ...
Rl)- 8 g 71 about 19% by weight of solids. The mixture also had a ratio of 2.6 mols of potassium hydroxide per mol of bisphenol-A.
polyformal was obtained consisting of chemically combined bis-phenol-A units and formaldehyde units having an lntrlnsic vis-cosity of about 0.50 dl/~. A tough flexible film was obtained from the polyformal following the abovP described casting or compression molding techniques.
Example 5.
The procedure of Example 4 was repeated, except that in place of the potassium hydroxide there was utili~ed 2.1 mols sodium hydroxide per mol of bisphenol-A. After approximately one hour, there was recovered a 66% yield of a pol~formal ~aving an intrinsic viscosity o 0.80 dl/g.
Example 6.
The procedure of Example 4 was repeated, except t~lat there was utilized in the mixture 1% by weight of p t-butyl-phenol, based on the weight of bisphenol A and the mi~ture ~;!as heated for 105 minutes at 70C. No Aliqtlat phase transfPr catalyst was used. There was obtained a polyformal ha-~ing an ~0 i.ntrinsic viscosity of 0.352 in chloroform at 2SC and consi.stlng essentially of chemically combined bisphenol-A uni~ and or-maldehyde units and chain stopped with p-t--butylphenol urlits.
The resulting polyformal was cast or compression molded to a tough flexible film.
The above procedure was repeated, except tha-~ 2V/~ by weight of the chain stopper wa5 used in the intercondensatio mixture. Tt was found that the intrinsic viscosity of the polyformal had been reduced to 0.273. A further interconden-sation reaction was attempted, free of chain-s~.opper ~sing stoichiometric amounts of potassium hydroxide and ~he bis phenol-A. It was found that even though ~he mixture had been , . , : . . ,.:. , ., , , - . :
.. . .. .. . . . .. .
~ 4~Y RD~8971 heated and stlrred for two hours at 70C, the intrin~lc vls-cosity of the resulting polyformal was 0.22.7. ~he low ln~rin-sic viscosity of the polyformal indicated that even though the intercondensation reaction mixture was freP of chain s~opper and it had been heated for two hours, more than a stoichio~
metric amount of potassium hydroxide was needed to produce polyformal having an intrinsic viscoslty of at leas~ 0.3 dl/g. ;
Example 7.
A mixture of methylene bromide, potassium hydroxide pellets, bisphenol-A and Aliquat phase transfer catalyst ~as `~
heated for 10 minutes at 96C under substanti.ally anhydrous conditions while the mixture was stirred. The mixture con~ained 11% by weight of solids and the potassium hydroxide was utllized in a proportion of 4 mols of potassium hydroxide per mol of bisphenol-A while the phase transfer catalyst was employe~ in a proportion of 0.1 mol of catalyst per mol of bisphenol-A
There was obtained a polyformal consisting essentially of chem-ically combined bisphenol-A units and formaldehyde lmirs having an intrin~ic viscosity in chlorofo~m of 1.9 at 25C.
The polymer was cast or compression mold~d to a tough 1exlble film.
Example 8.
A mixture of methylene bromide, 1,1-~ichloro-2,2-bis (4-hydroxyphenyl)ethylene, potassium hydroxide pellets and Aliquat phase transfer catalyst was heated and stirxed at 96C
for a period of 75 minutes under substantially anhydrous con-ditions. There was obtained a polyformal consistirlg essen~ially of formaldehyde units chemically combined with units of the formula, -0 ~ C ~ o_ ~C~
Cl Cl .. . .
~ ~ 7 ~ ~ ~ RD-8971 and having an intrinsic viscosity o 0.441. The polymer was readily converted to a tough flexible film by casting from chloroform solution or by compression molding. It had a Tg of 115C. .
S The above film exhibits valuable dlelectrlc and fl~me retardant properties qualifying it as a Elame retardant addi~ive in injection moldable plastics. The film o~gen inde~ i8 37.
Example 9.
A mixture of 16 parts (0.05 mol) of 2,2-bis(p-hydroxy-phenyl)-l,l,l-trichloroethane, ll parts ~O.lg5 mol) o:E K0~1 pellets, 56 parts of methylene bromide and 66 parts of N--methyl~
pyrrolidone was stirred at reflux (70~C). A vigorous reactio with obvious exotherm and increased reaction mixture viscosity was apparent after 13 minutes. After 51 minutes the reac~io mixture was poured into methanol and the polymer was isolated in the usual manner. There was obtained a 75% yield or a poly-formal consisting essentially of formald~hyde units chemically combined with units of the formula, -o~ C~ O , `' `''' Cl~ ~Cl and having an intrinsic viscosity of ~.745 dl/g.
Example 10.
A mixture of methylene chloride, N-methylpyrrolidone, potassium hydroxid~e pellets and 9,9-bis(4-hydroxyphenyl)flllorene, or "BPF", was stirred for 66 minutes at 70C under sub3tantially anhydrous conditions. There was obtained a polyformal having an intrinsic viscosity of 0.638 and consisting essentially of chemically combined formaldehyde units and ur~its o the formula3 Z~7 _o~ ~0- ~'~
The polyformal was obtained at a 63% yield and formed a tough flexible film by casting or com~ression molding. I~
had a Tg of 221C. `
Example 11.
A mixture of 2.3 parts (0.01 mol) of bis~henol-A, 1.7 parts (0.026 mol) of 85% pulverized potas3ium hydroxide, 0.47 part (0.001 mol) of Aliquat 336 and about 53 ~arts o~ methylene ; chloride were stirred at room temperature un~er substantially anhydrous conditions for 18 hours. The r~action mixture was then washed with water until it was neutral. Methanol was then added to the mixture resulting in the precipitation or product.
There was obtained a 49% yield o polyformal having an intrinsic viscosity of 0.31 dl/g, consisting essentially of chemically combined bisphenol-A units and formaldehyde units.
Example 12.
A mixture was stirred in a closed system at 50~ con-sisting of 3600 parts of methylene chloride, 119 parts (0.238 mol~ of Ali~uat 336, 542 parts (2.37 mols) o~ bisphenol-A and 400 parts (6.2 mols) of potassium hydroxide pellets. The mix-ture w~s stirred for about 115 minute~. There was obtained a polyformal, consisting essentially of chemically combined bisphenol-A units and formaldehyde units having an intrinslc viscoisty of 0.551 di/g.
Example 13.
z~
.
: A mixture of methylene chloride, N-methylpyrrolidone, potassium hydroxide pellets and 2,2-bls(4-hydroxyphenyl~-butane was stirred at 70C under substantially anhydrous conditiolls for 30 minutes. The mixture had a solids content of about 15% by weight and there was used a proportion of about 52 parts ~ :
of methylene chloride per 60 parts of N-methylpyrrolidone and a ratio of 2.6 mols of potassium hydroxide per mol of ~he 2,2-bis(4-hydroxyphenylj-butane. There was obtained a poly-formal consisting essentially of chemically combined formalde-hyde units and units of the formula, - O ~ C ~ O-and having an intrinsic viscosity of 1.48 and a Tg of 86~C.
Example 14.
A mixture of methylene chloride, N-methylpy~olidone, bisphenol-A, 0-hydroxyethylresorcinol and potassium hydroxlde pellets was stirred at a temperature of 70C for 90 m:Lnlltes under substantially anhydrous conditions. The mix~ur~ had a solids content of l9~/~ by weight and there was utilized a pro~
portion of about 78 parts of methylene chloride per 91 parts of the N-methylpyrrolidone, and a ratio of about 2.6 mols vf potassium hydroxide per mol of bisphenol-A and a proportion of about 35 mols o-f bisphenol-A per mol o 0-hydroxyethyl-resorcinol. There was obtained a polyformal consistiIlg ~ssen tially of chemically combined bisphenol-A units and fnrmalde-hyde units and chain terminated with units of the formul~, HO~H2CH2 ~0- .
.
: : . .- . ~ . , .
having an intrinsic viscosi-ty o~ 0.471 dl/g Example ~ .
A mixture was ~.irr~d under sub~tanti.ally anhydrou~
conditions consisting of methyl~ne chloride, N-methylpyrroli done, potassium hydroxide pellets, and 3,3-bis(p-hydroxy~hPnyl) pentane for a period of about 42 minutes at a temperature of 70C. The mixture had a solid~ content of aboutl8 % by weight and a ratio of about 52 parts of methylene chloride per 60 parts of N-methylpyrrolidone and a proportion o about 2.6 mols of potassium hydroxide per mol of the 3,3~bis~p~h~drs~xy-phenyl)-pentane. There was obtaine.d a polyvr~1al h~Villg a'L~
intrinsic viscosity of 0.831 dl/g, a T of ~1C and conslsting g .
essentially of chemically combined rormaldehyde ~mits and ~mi~3 of the formula, -o ~ C ~ 0 Example 16.
A mixture of methylene chloridP, ~hlorobenze~e, potassium hydroxide pellets, bisphenol-A and Ali~uat, the phase transfer catalyst o~ Example l, manufactured by the General Mills Company, Chemical Division, was heat~d and stirred fcr a period o 7.4 hours at a temperature of 60C unde~ a nitrogen atmosphere. The sollds content of the mixture was about 20% by weight and there was u~ilized a mol -ra~io o~ 2.
mols of potassium hydroxide per mol o~ bisphenol-.A. There wa3 also utilized in the mixture, a proportion of about 11~0 part~
of chlorobenzene to 901 parts of methylene chloride. In addi.tion J
the Allquat was employed in the mixtur at a proportion of 0.1 mol of Aliquat per mol of bisphenol-A.
Following the procedure of Exa~ple 1, there was recovered a 58 % yield of a polyformal havi~g an inkrinsic viscosity of 0.735 dl/~ in chloroform at 25. A c]ear fllm was obtained by casting the polymer from a chloroform solution or compression molding it at 160C. The film is tough and flex-ible and exhiblts a Gardner impact value of ~r~ater than 320 in. lb.
~xample 17.
The procedure of Example 16 was repeated, except ~hat ln place of the potasslum hydroxlde there was util.i~ed 4 mols of sodium hydroxide. In additionl there was utlliæed a proporti~n of about 68 parts of chlorobenzene to 20 parts of the mPthylene chloride. The intercondensation reactioll was conducted at a tem-perature of 75C and it was completPd within ~ h3urs~ There was obtained a 75% yield of a polyformal consisting essentially of chemically combined formaldehyde units and bisphenol-~ units, as shown by Example 1, having an intrinsic viscoslty of 0.422 dl/g. A tough flexible film was obtained by castin~ the pol~mer from chloroform or compression molding it in accordance wlth the procedure of Example 1.
Example 18, The procedure of Example 7 utilizlng methylene bromide was repeated except that in place o blspheno`l-A thare was used CH ~ CH3 -15~
, .
. , ; : .;. :. . :
There was obtained a polyformal having a Tg of 175C and con-sisting essentially of chemically combined ~mit~ of th~ formula, _oH ~ S ~ OCH2-Example 19.
.
A mixture of 30 parts ~0.1 mol) of 3,4-bis(p-hydroxy-phenyl~-3,4-hexanediol, 14.6 parts (0.26 mol) KOH pellets, 81 part~ methylene chloride and 93 parts of N-meth~lpyrrolidone was stirred and heated at reflux (70C~. A~ter 81 minutes, 11 parts (0.2 mol) more of KOH pellets was added. AEter 92 minutes the very thick reaction mixture was pourecl into methanrJl to recover the polymer. A film formlng polyforrnal was ob~alnecl, consisting of formaldehyde units chemically comblned with units of the structure C,H3 A CH~
-O ~ C-OH
f~~
HOC ~ O-,CH2 ~H3 The polymer had an intrinsic viscosity of 0.5~4 dl/g, and ~g of 67C. , . Although N-methylpyrrolidone was used to r.nake the ~ `~
a~Dove polyformal,the present invention provides ~or ~he use o a broad variety of dipolar aprotic solvents which can be used in the poly~ormal reaction mixture at 25C to lQOC, and a~
4,4'-dihydroxy-3,3',5,5'-tetramethylbiphenyl; ~:
2,4'-dihydroxybenzophenone;
4,4'-dihydroxydiphenylsulfone;
2,4'-dihydroxydiphenylsulfone;
4,4'-dihydroxydiphenyl sulfoxide;
4,4'-d-~h~droxydiphenyl sulfide;
hydroquinone;
resorcinol;
9,9-bis(4-hydroxyphenyl)-fluorene 3,4'-dihydroxydiphenylmethane;
4,4'-dihydroxybenzophenone;
4,4'-dihydroxydiphenylether;
1,1-dichloro-2,2~bis(4-hydroxyphenyl)ethylene, and 1,1,1-trichloro-2,2-bis(4-hydroxyphenyl)ethane.
Methylene halides which can be used in the practice of the invention, are, for example, methylene chloride, methylene bromide, chlorobromo methane, etc. Alkali hydroxldes which can be employed in the practice of the invention are, for example, potassium hydroxide whi~h can be in the form of pellets, powder, etc., sodium hydroxide, etc.
The polyformal resins having units of ormula (1~ are :~
thermoplastic injection moldable materials which can be con-verted to films and fibers. Preferably, the poly~ormal resins are transparent injection moldable film forming and fiber form~
ing thermoplastic materials. In particular instances, the poly-formal resins of the present invention may bP translucent or cloudy materials, depending on the degree o crystallization of the resulting polymer.
The polyformal resins of the present invention also can be phosgenated to produce polyformal~polycarbonate copolymers.
The polyformals of formula (13 and the polyformal-polycarbonate copolymers can be further blended with other thermoplastic organic resins, such as Lexan ~ resin, PPO ~D resin, Valox ~
resin, all products of the General Electric Company, over wide proportions by weight, such as from 1% ~o 99% of the polyformal resin to 9g% to 1% of the high perfo~mance thermoplastic organic resin. The polyformal reslns of the present invention also can be blended with various fillers, such as glass fiber, silicon carbide whiskers, silica fillers, etc., stabilizers, pigments t flame retardants , etc.
In the practice of the inventi.on, the polyformal resin can be made by effecting contact at a temperature of 0C
to 100C and preferably 40C to 100C between methylene halide and blspheno' in the presence of alksli hydroxide. Reaction can be conducted between excess methylene halide and blsph~nol until the latter has been completely reacted.
Reaction between the methylene halide and the bisphenol can be effected under substantially anhydrous conditions.
Reflux temperatures at atmospheric pressure or above atmospheri.c pressure can be used along with agitation of the mixture. Re2c-tion between methylene halide and bisphenol in the presene of excess alkali hydroxide can be accel~rated by using a substan-tially inert organic solvent in combination with methylene halide, such as a nonpolar or dipolar aprotic organic solvent. Nonpolar organic solvents which can be employed in the methylene halide are, for example, chlorobenzene, dichlorobenzene, benzenQ, toiuene, etc. In addition, there can be used dipolar aprot:ic solvents, such as N-methylpyrrolidone, tetrahydrofuran, dimethylsulfoxide, etc.
Experience has shown that when methylene halide is employed in the absence of a dipolar aprotic solvent, effec~ive results are achieved if a phase transfer catalyst is used to facilitate in situ formation of the alkali salt of the bisphenol and the subsequent condensation reaction with the methylene halide. Suitable phase transfer catalysts are, for examPle, 3.~ 4~7 R~-8971 quaternary ammonium and phosphonlum salts, such as describ~d in JACS 93, 195 (1971) by C.M. Starks. A proportion o~ from about 0.01 to 0.5 mols of the phase transfer catalyst pe.r mol of the bls phenol has been found to provide for effective results, and preferably from 0.02 to 0.10 mols of phase transfer catalyst per mol o bisphenol can be employed.
The intercondensation reaction can be conduc~ed over a period of from 0.1 hours to 24 hours cr greater depetld^ing upor such factors as the nature of the methylene halide, whether an organic solvent is employed in combination with the methylel~e halide,the type of such organi.c solvent, temperature of the reao~
tion, the degree o~ agitation, etc. In particular instances, for example, the more hignly reactive methylene bromide carL b~
substituted for methylene chloride or a mi~ture OL Ctll.OrO~enZen?, with methylene chloride will reflux at a higher temperature. '.
In addition, the reaction can be conducted at elevated pressu-res, or in a closed system to permit the methylene halide ~o xeact with the bisphenol at a higher temperature. Those skilled :in the art would know, for example, that the methylen.e halide itself, when used in excess amo~nts, can serve as a suitab`le organic solven~ as well as a reactant.
The foll.owing examples are given by way of :illustr~
tion and not by way of limitation. All parts are by w~i~ht, unless otherwise speceified.
Example 1.
A mixture of 114 parts ~a. 5 mol) of bisphenol-A, 95 parts (1.7 mol) KOH pellets, 23.3 parts (.05 mol) of ~`~ Aliquat 336 (95% ac~ive monomethyltrlcaprylyl ammonium chloride), a phase transfer catalys~ of the General Mi.lls Co~pany, and 1,009 par~s of methylene chloride was refluxed and s~irred ~-8971 for a period of 21 hours under a nitrogen atmosphere. Wate-r was then added to the mixture and the organic phase was separ-ated and washed with water. A 70% yield of polymer was obtained by adding the organic layer to methanol and filterin~ and dry-ing the resulting precipitate at 60C. ThP polymer was found tohave a Tg of 85C and an intrinsic viscosity o 0.60 dl~g in chloroform at 25C. The polymer was compression molded at 160C
to produce a tough colorless, f~exible transparent film. It also can be cast from chloroform. Eased on elemental anal~sis and ~MR spectrum, the pol~mer was a poly~ormal having t~e formllla ~ Q ~ C ~ CH2~-where n has an average value of 65.
The polyformal had the following p~ysical propert.ies:
Tensile strength, p.s.i. at yield 7-8000 Tensile strength, p. 5. i. at break 7100-7S00 Elongation % 110 Density g/cm3 1.10 Flexural strength p.s.i. 14,3~0 Flexural modulus 105 p.s.i. 73F 4 1 Gardner impac~ stre~gth ~320 in. lb.
Example 2.
A mixture o dimethylsulfoxide, me-thyl~ne chloride, potassium hydroxide, bisphenol-A, and Ali~ at ~7as stirred at a temperature of 60C for 4 hours under substantially anhydrous conditions. The mixture had a weight percent solids oE ~2~/~ and a ratio of aboutllOparts of dimethyl sulfoxide per 90 par~s of methylene chloride. In addition, there was utilized in the mixture a ratio of 2.6 mols of potassium hydroxide per mol of ~ Y24~ RD-8g71 the bisphenol-A while the Aliquat was employed in a proportion of about 0.1 mol of Aliquat per mol of the bisphenol-A. There was obtained a polyformal having an intrinsic Yiscosiky o~
0.548 dl/g in chloroform at 25C. Based on method o~ prepara tion, the polymer consisted essenti.ally of chemically combined blsphenol-A units and formaldehyde units. A tough flexible film was obtained by compression molding, following the ~rocedure of ~
~:xam~le 1, or by casting from a chloroform solution. ~.
Example 3.
A mixture of chlorobenzene, rnethylene chloride, potas-sium hydroxide pellets, bisphenol-A, tetrabutylammonium bromlde and 1.9% by weight of water was stirred at 75C or a period of about 40 minutes. The mixture had a 19% solids content by weight, where the chlorobenzene was utilized in a proportion o:E
about 3 parts o~ chlorobenzene per part of methylene chloride 9 while there was employed about 2.6 mols of potassium hydroxide per mol cf bisphenol-A. In addition, the tetrabutyla~mvnium bromide was present in the mixture in a proportion of ,~bout 0.1 mol of the phase transfer catalyst per mol of bisphenol-A.
There was obtained a 36% yield of polyformal from the above mixture having an intrinsic viscosity of 0.519 dl/g in chloroform at 25C and consisting essentially of chemically combined bisphenol-A units and formaldehyde units. A ~ough flexible film was obtained by casting or compression molding the ~lymer following the procedure previo~sly described. `:
Example 4.
A mixture of N-methylpyrrolidone, methylene chloride, potassium hydroxide pellets and bisphenol-A was stirred for 39 minutes at 70C under substan~ially anhydrous conditions. The N-methylpyrrolidone and the methylene chloride was used in abou~
equal proportions by weight in the polymerization ~ixture having ,. ,,... ....... .. , , ...... ,,,, ~ . . .. ...
Rl)- 8 g 71 about 19% by weight of solids. The mixture also had a ratio of 2.6 mols of potassium hydroxide per mol of bisphenol-A.
polyformal was obtained consisting of chemically combined bis-phenol-A units and formaldehyde units having an lntrlnsic vis-cosity of about 0.50 dl/~. A tough flexible film was obtained from the polyformal following the abovP described casting or compression molding techniques.
Example 5.
The procedure of Example 4 was repeated, except that in place of the potassium hydroxide there was utili~ed 2.1 mols sodium hydroxide per mol of bisphenol-A. After approximately one hour, there was recovered a 66% yield of a pol~formal ~aving an intrinsic viscosity o 0.80 dl/g.
Example 6.
The procedure of Example 4 was repeated, except t~lat there was utilized in the mixture 1% by weight of p t-butyl-phenol, based on the weight of bisphenol A and the mi~ture ~;!as heated for 105 minutes at 70C. No Aliqtlat phase transfPr catalyst was used. There was obtained a polyformal ha-~ing an ~0 i.ntrinsic viscosity of 0.352 in chloroform at 2SC and consi.stlng essentially of chemically combined bisphenol-A uni~ and or-maldehyde units and chain stopped with p-t--butylphenol urlits.
The resulting polyformal was cast or compression molded to a tough flexible film.
The above procedure was repeated, except tha-~ 2V/~ by weight of the chain stopper wa5 used in the intercondensatio mixture. Tt was found that the intrinsic viscosity of the polyformal had been reduced to 0.273. A further interconden-sation reaction was attempted, free of chain-s~.opper ~sing stoichiometric amounts of potassium hydroxide and ~he bis phenol-A. It was found that even though ~he mixture had been , . , : . . ,.:. , ., , , - . :
.. . .. .. . . . .. .
~ 4~Y RD~8971 heated and stlrred for two hours at 70C, the intrin~lc vls-cosity of the resulting polyformal was 0.22.7. ~he low ln~rin-sic viscosity of the polyformal indicated that even though the intercondensation reaction mixture was freP of chain s~opper and it had been heated for two hours, more than a stoichio~
metric amount of potassium hydroxide was needed to produce polyformal having an intrinsic viscoslty of at leas~ 0.3 dl/g. ;
Example 7.
A mixture of methylene bromide, potassium hydroxide pellets, bisphenol-A and Aliquat phase transfer catalyst ~as `~
heated for 10 minutes at 96C under substanti.ally anhydrous conditions while the mixture was stirred. The mixture con~ained 11% by weight of solids and the potassium hydroxide was utllized in a proportion of 4 mols of potassium hydroxide per mol of bisphenol-A while the phase transfer catalyst was employe~ in a proportion of 0.1 mol of catalyst per mol of bisphenol-A
There was obtained a polyformal consisting essentially of chem-ically combined bisphenol-A units and formaldehyde lmirs having an intrin~ic viscosity in chlorofo~m of 1.9 at 25C.
The polymer was cast or compression mold~d to a tough 1exlble film.
Example 8.
A mixture of methylene bromide, 1,1-~ichloro-2,2-bis (4-hydroxyphenyl)ethylene, potassium hydroxide pellets and Aliquat phase transfer catalyst was heated and stirxed at 96C
for a period of 75 minutes under substantially anhydrous con-ditions. There was obtained a polyformal consistirlg essen~ially of formaldehyde units chemically combined with units of the formula, -0 ~ C ~ o_ ~C~
Cl Cl .. . .
~ ~ 7 ~ ~ ~ RD-8971 and having an intrinsic viscosity o 0.441. The polymer was readily converted to a tough flexible film by casting from chloroform solution or by compression molding. It had a Tg of 115C. .
S The above film exhibits valuable dlelectrlc and fl~me retardant properties qualifying it as a Elame retardant addi~ive in injection moldable plastics. The film o~gen inde~ i8 37.
Example 9.
A mixture of 16 parts (0.05 mol) of 2,2-bis(p-hydroxy-phenyl)-l,l,l-trichloroethane, ll parts ~O.lg5 mol) o:E K0~1 pellets, 56 parts of methylene bromide and 66 parts of N--methyl~
pyrrolidone was stirred at reflux (70~C). A vigorous reactio with obvious exotherm and increased reaction mixture viscosity was apparent after 13 minutes. After 51 minutes the reac~io mixture was poured into methanol and the polymer was isolated in the usual manner. There was obtained a 75% yield or a poly-formal consisting essentially of formald~hyde units chemically combined with units of the formula, -o~ C~ O , `' `''' Cl~ ~Cl and having an intrinsic viscosity of ~.745 dl/g.
Example 10.
A mixture of methylene chloride, N-methylpyrrolidone, potassium hydroxid~e pellets and 9,9-bis(4-hydroxyphenyl)flllorene, or "BPF", was stirred for 66 minutes at 70C under sub3tantially anhydrous conditions. There was obtained a polyformal having an intrinsic viscosity of 0.638 and consisting essentially of chemically combined formaldehyde units and ur~its o the formula3 Z~7 _o~ ~0- ~'~
The polyformal was obtained at a 63% yield and formed a tough flexible film by casting or com~ression molding. I~
had a Tg of 221C. `
Example 11.
A mixture of 2.3 parts (0.01 mol) of bis~henol-A, 1.7 parts (0.026 mol) of 85% pulverized potas3ium hydroxide, 0.47 part (0.001 mol) of Aliquat 336 and about 53 ~arts o~ methylene ; chloride were stirred at room temperature un~er substantially anhydrous conditions for 18 hours. The r~action mixture was then washed with water until it was neutral. Methanol was then added to the mixture resulting in the precipitation or product.
There was obtained a 49% yield o polyformal having an intrinsic viscosity of 0.31 dl/g, consisting essentially of chemically combined bisphenol-A units and formaldehyde units.
Example 12.
A mixture was stirred in a closed system at 50~ con-sisting of 3600 parts of methylene chloride, 119 parts (0.238 mol~ of Ali~uat 336, 542 parts (2.37 mols) o~ bisphenol-A and 400 parts (6.2 mols) of potassium hydroxide pellets. The mix-ture w~s stirred for about 115 minute~. There was obtained a polyformal, consisting essentially of chemically combined bisphenol-A units and formaldehyde units having an intrinslc viscoisty of 0.551 di/g.
Example 13.
z~
.
: A mixture of methylene chloride, N-methylpyrrolidone, potassium hydroxide pellets and 2,2-bls(4-hydroxyphenyl~-butane was stirred at 70C under substantially anhydrous conditiolls for 30 minutes. The mixture had a solids content of about 15% by weight and there was used a proportion of about 52 parts ~ :
of methylene chloride per 60 parts of N-methylpyrrolidone and a ratio of 2.6 mols of potassium hydroxide per mol of ~he 2,2-bis(4-hydroxyphenylj-butane. There was obtained a poly-formal consisting essentially of chemically combined formalde-hyde units and units of the formula, - O ~ C ~ O-and having an intrinsic viscosity of 1.48 and a Tg of 86~C.
Example 14.
A mixture of methylene chloride, N-methylpy~olidone, bisphenol-A, 0-hydroxyethylresorcinol and potassium hydroxlde pellets was stirred at a temperature of 70C for 90 m:Lnlltes under substantially anhydrous conditions. The mix~ur~ had a solids content of l9~/~ by weight and there was utilized a pro~
portion of about 78 parts of methylene chloride per 91 parts of the N-methylpyrrolidone, and a ratio of about 2.6 mols vf potassium hydroxide per mol of bisphenol-A and a proportion of about 35 mols o-f bisphenol-A per mol o 0-hydroxyethyl-resorcinol. There was obtained a polyformal consistiIlg ~ssen tially of chemically combined bisphenol-A units and fnrmalde-hyde units and chain terminated with units of the formul~, HO~H2CH2 ~0- .
.
: : . .- . ~ . , .
having an intrinsic viscosi-ty o~ 0.471 dl/g Example ~ .
A mixture was ~.irr~d under sub~tanti.ally anhydrou~
conditions consisting of methyl~ne chloride, N-methylpyrroli done, potassium hydroxide pellets, and 3,3-bis(p-hydroxy~hPnyl) pentane for a period of about 42 minutes at a temperature of 70C. The mixture had a solid~ content of aboutl8 % by weight and a ratio of about 52 parts of methylene chloride per 60 parts of N-methylpyrrolidone and a proportion o about 2.6 mols of potassium hydroxide per mol of the 3,3~bis~p~h~drs~xy-phenyl)-pentane. There was obtaine.d a polyvr~1al h~Villg a'L~
intrinsic viscosity of 0.831 dl/g, a T of ~1C and conslsting g .
essentially of chemically combined rormaldehyde ~mits and ~mi~3 of the formula, -o ~ C ~ 0 Example 16.
A mixture of methylene chloridP, ~hlorobenze~e, potassium hydroxide pellets, bisphenol-A and Ali~uat, the phase transfer catalyst o~ Example l, manufactured by the General Mills Company, Chemical Division, was heat~d and stirred fcr a period o 7.4 hours at a temperature of 60C unde~ a nitrogen atmosphere. The sollds content of the mixture was about 20% by weight and there was u~ilized a mol -ra~io o~ 2.
mols of potassium hydroxide per mol o~ bisphenol-.A. There wa3 also utilized in the mixture, a proportion of about 11~0 part~
of chlorobenzene to 901 parts of methylene chloride. In addi.tion J
the Allquat was employed in the mixtur at a proportion of 0.1 mol of Aliquat per mol of bisphenol-A.
Following the procedure of Exa~ple 1, there was recovered a 58 % yield of a polyformal havi~g an inkrinsic viscosity of 0.735 dl/~ in chloroform at 25. A c]ear fllm was obtained by casting the polymer from a chloroform solution or compression molding it at 160C. The film is tough and flex-ible and exhiblts a Gardner impact value of ~r~ater than 320 in. lb.
~xample 17.
The procedure of Example 16 was repeated, except ~hat ln place of the potasslum hydroxlde there was util.i~ed 4 mols of sodium hydroxide. In additionl there was utlliæed a proporti~n of about 68 parts of chlorobenzene to 20 parts of the mPthylene chloride. The intercondensation reactioll was conducted at a tem-perature of 75C and it was completPd within ~ h3urs~ There was obtained a 75% yield of a polyformal consisting essentially of chemically combined formaldehyde units and bisphenol-~ units, as shown by Example 1, having an intrinsic viscoslty of 0.422 dl/g. A tough flexible film was obtained by castin~ the pol~mer from chloroform or compression molding it in accordance wlth the procedure of Example 1.
Example 18, The procedure of Example 7 utilizlng methylene bromide was repeated except that in place o blspheno`l-A thare was used CH ~ CH3 -15~
, .
. , ; : .;. :. . :
There was obtained a polyformal having a Tg of 175C and con-sisting essentially of chemically combined ~mit~ of th~ formula, _oH ~ S ~ OCH2-Example 19.
.
A mixture of 30 parts ~0.1 mol) of 3,4-bis(p-hydroxy-phenyl~-3,4-hexanediol, 14.6 parts (0.26 mol) KOH pellets, 81 part~ methylene chloride and 93 parts of N-meth~lpyrrolidone was stirred and heated at reflux (70C~. A~ter 81 minutes, 11 parts (0.2 mol) more of KOH pellets was added. AEter 92 minutes the very thick reaction mixture was pourecl into methanrJl to recover the polymer. A film formlng polyforrnal was ob~alnecl, consisting of formaldehyde units chemically comblned with units of the structure C,H3 A CH~
-O ~ C-OH
f~~
HOC ~ O-,CH2 ~H3 The polymer had an intrinsic viscosity of 0.5~4 dl/g, and ~g of 67C. , . Although N-methylpyrrolidone was used to r.nake the ~ `~
a~Dove polyformal,the present invention provides ~or ~he use o a broad variety of dipolar aprotic solvents which can be used in the poly~ormal reaction mixture at 25C to lQOC, and a~
5% to 95,JO by weight, based on the ~.otal weight of the nixture.
Although the above examples are limi.~ed to only a ~ -~ew of the very many variables whlch can be e~plvyed in the practice of the present invention, it should be understood that the present invention is directed to a much broader class of polyformals included by formula (1~ as well as procedures used in making these materials as shown in the description S preceding these examples.
.. .. ~ ....
Although the above examples are limi.~ed to only a ~ -~ew of the very many variables whlch can be e~plvyed in the practice of the present invention, it should be understood that the present invention is directed to a much broader class of polyformals included by formula (1~ as well as procedures used in making these materials as shown in the description S preceding these examples.
.. .. ~ ....
Claims (15)
1. A method for making a polyformal consisting essentially of chemically combined units of the formula where R is a divalent C(6-30) aromatic radical, comprising agitating under substantially anhydrous conditions a reaction mixture containing as essential ingredients methylene halide, bisphenol, alkali hydroxide and a member selected from the class consisting of a phase transfer catalyst and a dipolar aprotic solvent, where there is utilized in the reaction mixture per mole of bisphenol more than 1 mole of methylene halide and more than 2 moles of alkali hydroxide, resulting in a reaction mixture less sensitive to water and other impurities containing hydroxy groups.
2. A method in accordance with claim 1, where the methylene halide is methylene chloride.
3. A method in accordance with claim 1, where the methylene halide is methylene bromide.
4. A method in accordance with claim 1, where a phase transfer catalyst is utilized in the reaction mixture.
5. A method in accordance with claim 1, where a substantially inert non-polar organic solvent is utilized in the reaction mixture.
6. A method in accordance with claim 5, where chlorobenzene is utilized in the reaction mixture.
7. A method in accordance with claim 5, where N-methylpyrrolidone is utilized in the reaction mixture.
8. A method in accordance with claim 1, where dimethylsulfoxide is utilized in the reaction mixture.
9. A method in accordance with claim 1, where a temperature in the range of from 40°C to 100°C is employed.
10. A method for making a polyformal consisting essentially of chemically combined units of the formula comprising agitating under substantially anhydrous conditions a reaction mixture containing as essential ingredients methylene chloride, bisphenol-A, potassium hydroxide and a member selected from the class consisting of N-methylpyrrolidone and monomethyltricaprylyl ammonium chloride at a temperature in the range of from 0°C to 100°C, where there is utilized in the reaction mixture per mole of bisphenol-A more than 1 mole of methylene chloride and more than 2 moles of potassium hydroxide.
11. A method for making a polyformal consisting essentially of chemically combined units of the formula comprising agitating under substantially anhydrous conditions a reaction mixture containing as essential ingredients methylene chloride, a bisphenol of the formula potassium hydroxide and a member selected from the class consisting of N-methylpyrrolidone and monomethyltricaprylyl ammonium chloride at a temperature in the range of from 0°C
to 100°C, where there is utili7ed in the reaction mixture per mole of bisphenol more than 1 mole of methylene chloride and more than 2 moles of potassium hydroxide.
to 100°C, where there is utili7ed in the reaction mixture per mole of bisphenol more than 1 mole of methylene chloride and more than 2 moles of potassium hydroxide.
12. A method in accordance with claim 10 or 11, where monomethyl tricaprylyl ammonium chloride is present in the reaction mixture.
13. A method in accordance with claim 10 or 11, where N-methylpyrrolidone is employed in the reaction mixture.
14. A method in accordance with claim 10 or 11, where chlorobenzene is employed in the reaction mixture.
15. A polyformal consisting of chemically combined units of the formula
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US73956276A | 1976-11-08 | 1976-11-08 | |
| US739,562 | 1976-11-08 |
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| CA1117247A true CA1117247A (en) | 1982-01-26 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000289785A Expired CA1117247A (en) | 1976-11-08 | 1977-10-28 | Film forming, moldable aromatic polyformal resins and method for making same |
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|---|---|
| JP (1) | JPS5358600A (en) |
| CA (1) | CA1117247A (en) |
| DE (1) | DE2738962A1 (en) |
| FR (1) | FR2370066A1 (en) |
| GB (1) | GB1555384A (en) |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7199208B2 (en) | 2003-07-25 | 2007-04-03 | Bayer Materialscience Ag | Polyformals and copolyformals with reduced water absorption, production and use thereof |
| US7208564B2 (en) | 2003-08-27 | 2007-04-24 | Bayer Materialscience Ag | Branched polyformals and copolyformals their preparation and use |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54125297A (en) * | 1978-03-23 | 1979-09-28 | Gen Electric | Preparation of polyformal and products thereof |
| JPS5674125A (en) * | 1979-10-29 | 1981-06-19 | Kanegafuchi Chem Ind Co Ltd | Novel polyether resin and its preparation |
| JPS5747328A (en) * | 1980-09-05 | 1982-03-18 | Kanegafuchi Chem Ind Co Ltd | Novel polyether resin and its production |
| US4345051A (en) * | 1981-03-02 | 1982-08-17 | General Electric Company | Block copolymers of polyphenylene oxides and polyformals of sterically-hindered dihydric phenols |
| US4345050A (en) * | 1981-03-02 | 1982-08-17 | General Electric Company | Block copolymers of polyphenylene oxides and polyformals on non-sterically-hindered dihydric phenols |
| JPS57179221A (en) * | 1981-04-28 | 1982-11-04 | Kanegafuchi Chem Ind Co Ltd | Preparation of high-molecular weight polyether |
| WO1983003836A1 (en) * | 1982-05-04 | 1983-11-10 | General Electric Company | Block copolymers of polyphenylene oxides and polyformals of non-sterically-hindered dihydric phenols |
| US4544705A (en) * | 1983-04-18 | 1985-10-01 | Union Carbide Corporation | Aromatic polyformals |
| US4473684A (en) * | 1983-04-18 | 1984-09-25 | Union Carbide Corporation | Poly (aryl ether)s |
| US4497924A (en) * | 1983-04-18 | 1985-02-05 | Union Carbide Corporation | Aromatic polyformal blends |
| DE3725058A1 (en) * | 1987-07-29 | 1989-02-09 | Roehm Gmbh | THERMOPLASTICALLY PROCESSABLE POLYARYLENETHER WITH 9,9-BIS (4'-HYDROXYPHENYL) FLUORINE |
| JPH02124935A (en) * | 1988-11-04 | 1990-05-14 | Idemitsu Kosan Co Ltd | optical materials |
| DE4429107A1 (en) | 1994-08-17 | 1996-02-22 | Basf Ag | Molding compounds made from polyarylene ethers and copolyamides |
| DE19526855A1 (en) * | 1995-07-22 | 1997-01-23 | Basf Ag | Process for the preparation of polyarylene ethers with anhydride end groups |
| US7691477B2 (en) * | 2003-07-25 | 2010-04-06 | Bayer Materialscience Ag | Polyformals as a coextrusion protective layer on polycarbonate |
| EP2918623B1 (en) * | 2012-11-07 | 2022-04-06 | Mitsubishi Gas Chemical Company, Inc. | Polyformal resin copolymer and production method |
| RU2515987C1 (en) * | 2012-11-19 | 2014-05-20 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования Кабардино-Балкарский государственный университет им. Х.М. Бербекова (КБГУ) | Aromatic block-copolyethers |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3069386A (en) * | 1959-02-04 | 1962-12-18 | Union Carbide Corp | Thermoplastic aromatic polyformal resins and process for preparing same |
| US3442863A (en) * | 1964-06-10 | 1969-05-06 | Celanese Corp | Oxymethylene polymers containing units derived from chlorinated aromatic glycols and aldehydes |
| DE2258730A1 (en) * | 1971-12-01 | 1973-06-20 | Albright & Wilson | Polyarylene polyether - by reacting active dichloro cmpd with alkali metal salt of diphenol in aprotic polar solvent |
| GB1396990A (en) * | 1972-11-08 | 1975-06-11 | Ici Ltd | Aromatic polymer |
-
1977
- 1977-08-30 DE DE19772738962 patent/DE2738962A1/en not_active Withdrawn
- 1977-09-07 GB GB3740377A patent/GB1555384A/en not_active Expired
- 1977-09-22 JP JP11448777A patent/JPS5358600A/en active Pending
- 1977-10-26 FR FR7732234A patent/FR2370066A1/en active Pending
- 1977-10-26 SU SU772531953A patent/SU776564A3/en active
- 1977-10-28 CA CA000289785A patent/CA1117247A/en not_active Expired
- 1977-11-08 MX MX17124977A patent/MX145767A/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7199208B2 (en) | 2003-07-25 | 2007-04-03 | Bayer Materialscience Ag | Polyformals and copolyformals with reduced water absorption, production and use thereof |
| US7208564B2 (en) | 2003-08-27 | 2007-04-24 | Bayer Materialscience Ag | Branched polyformals and copolyformals their preparation and use |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5358600A (en) | 1978-05-26 |
| MX145767A (en) | 1982-03-29 |
| SU776564A3 (en) | 1980-10-30 |
| GB1555384A (en) | 1979-11-07 |
| FR2370066A1 (en) | 1978-06-02 |
| DE2738962A1 (en) | 1978-05-11 |
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