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    • 专利摘要:
    RD-8971 FILM FORMING, MOLDABLE AROMATIC POLYFORMAL RESINS AND METHOD FOR MAKING SAME The present invention relates to polyformal resins having an intrinsic viscosity of at least 0.3 in chloroform at 25.degree.C and a method for making such materials. The polyformal resins of the present invention are high molecular weight thermoplastic 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.
    公开号:SU776564A3
    申请号:SU772531953
    申请日:1977-10-26
    公开日:1980-10-30
    发明作者:Стюарт Хэй Аллан
    申请人:Дженерал Электрик Компани (Фирма)；
    IPC主号:
    专利说明:

    (54) METHOD FOR OBTAINING AROMATIC
    This invention relates to the preparation of polyformal resins, which are highly molecular thermoplastic resins suitable for each 5 injection-molding films (injection molding).
    A known method of producing aromatic polyformals by polycondensation of diphenols — sodium diphenol-iO with dihalomethylene in an organic solvent medium at 0-100 ° C. L.C
    The reaction is sensitive to small amounts of water and other impurities containing hydroxyl groups, which cause undesirable side reactions. As a result, polyformal resins obtained by a known method are characterized by extremely low viscosity.
    Polyformal unsuitable when used as a thermoplastic material due to its fragility and very low strength.
    The purpose of the present invention 25 is to increase the molecular weight of the polymers produced.
    The goal is achieved by using compounds of the general formula HO-R-OH (1), where R is 30 POLYFORMAL.
    a bivalent aromatic radical, and the process is carried out in the presence of alkali metal hydroxides and quaternary ammonium bases as catalysts.
    Some of the biophenols are the following compounds:
    2,2-bis- (4-hydroxyphenyl) propane, biophenol AJ
    2,4-dioxydiphenylmethane; bis (2-hydroxyphenyl) methane; 1,1-bis (4-hydroxyphenyl) ethane 1,1-bis (4-hydroxyphenyl) propane; 2,2-bis (4-hydroxyphenyl) -pentane; 3,3-bio- (4-hydroxyphenyl) -pentane; 4,4-dioxibisphenyl; 4/4-dioxy-3, 3; 5g-tetramethylphenyl, 2,4-dioxybenzophenone; 4,4-dioxydiphenylsulfone; 2, 4-dioxydiphenylsulfone, 4,4-dioxydiphenylsulfoxide; 4,4-dioxydiphenylsulfide; hydroquinone; resorcinol
    9,9-bis- (4-hydroxyphenyl) -fluorene; 3/4-dioxydiphenylmethane; 4,4-dioxybenzophenone; 4,4-dioxydiphenyl ether; 1,1-DICHLORO-2,2-bis- (4-oxnpheny, p) -ethylene; 1, 1,1-trichloro-2,2-bis- (4-hydroxyphenyl) -ethane Alkali metal hydroxides, which are used in practical cases, the invention is, for example, potassium hydroxide (these compounds are used in the form of granules, powder, etc.), as well as sodium hydroxide. Aromatic polyformal is obtained by making contact with, preferably from 4Q to 100 ° C, between dihalomethylene and biophenol in the presence of alkali hydroxide. Reactions are carried out between excess dihalomethylene and biophenol until the last of these two components is consumed. The reaction with dihalomethylene and bisphenol is carried out in practically no water conditions. The reflux temperatures under atmospheric or supernatural pressure are measured by mixing with a mixture of a reaction mixture. The reaction between the dihydrogen mide yen and biophenol in the presence of an excess amount of alkali metal hydroxide is accelerated by using a practically inert organic solvent in conjunction with the alkali metal hydroxide by using a practically inert organic solvent in conjunction with the alkali metal hydroxide, using a practically inert organic solvent in combination with an alkali metal hydroxide, by using a practically inert organic solvent in combination with an alkali metal hydroxide, by using a practically inert organic solvent in conjunction with an alkali metal hydroxide, using a practically inert organic solvent in conjunction with the alkali metal hydroxide, using a practically inert organic solvent in conjunction with the use of an alkali metal hydroxide by using a practically inert organic solvent in conjunction with the alkali metal hydroxide, using a practically inert organic solvent in combination with an alkali metal hydroxide by using a practically inert organic solvent in conjunction with the alkali metal hydroxide, using a practically inert organic solvent in combination with an alkali metal hydroxide. or dipolar aprotic organic solvent. The nonpolar organic solvents used in the process are, for example, chlorobenzene; dichlorobenzene, benzene, toluene, etc. Additionally, dipolar aprotic solvents such as methylpyrrolidone, tetrahydrofuran, dimethyl sulfoxide, etc. are used. If dimethyldihalomethyl is used without dipolar aprotic solvent, the effect is achieved if the Phase transfer catalyst is used to accelerate the formation of alkaline biophenol salts at the site and then carry out a condensation reaction with dihalomethyl. Suitable phase transfer catalysts are quaternary ammonium and phosphonium salts. The use of a phase transfer catalyst in amounts of from 0.01 to 0.5 mol per 1 mol of bisphenol provides good results, however, it is more preferable to use a phase skew analyzer in amounts of 0.02-0.10 mol per 1 mol of bispheiol. The reaction can be carried out within 0.1-24 hours or more depending on such factors; in kSh The nature of dngaloidmethylene depends on whether organic solvent is used in co4CTaFmH with dihalidemethylene on the type of organic solvent, rci-mp yni776564 of the reaction mixture and degree mixing. Example 1. A mixture consisting of 114 parts (0.5 mol) of biophenol A, 95 parts (1.7 mol) of KOH granules, 23.3 parts (0.05 mol) of 95% active monomethyltrikaprilil ammonium chloride (CMAX) catalyst phase transfer and 1.009 parts of dichloromethylene are subjected to refluxing and stirring for 21 hours in the atmosphere. Next, water is added to the mixture. The organic phase is separated and washed with water. A poly yield of 70% is achieved by adding an organic layer to methanol, followed by filtering and drying the resulting precipitate at a BO-c. The polymer obtained was found to be characterized by a glass transition temperature and intrinsic viscosity Of 6 dl / g in chloroform at. Polyester is molded under pressure, resulting in a durable, colorless, flexible transparent film. It can also be smelted from chloroform. The data of elemental analysis and analysis of the spectrum of nuclear magnetic resonance show that the polymer is a polyform characterized by forg tail where n is on average 65. The polyformal thus obtained is characterized by the following physical properties. Tensile strength (at yield) 0,492-562 kg / cm. Tensile strength (with destruction) 499t527 kg / sl; Relative lengthening, 110 Density, g / cm 1,10 Bending strength, kg / cm 1005 Elastic modulus, 1 kg / cm at 23 ,. 0.288 Example2. The mixture consisting of dimethylsulfoxide, dichloromethylene, sodium hydroxide, biofenrl A and the above MAX is subjected to stirring at 60 ° C for 4 hours almost under anhydrous conditions. In this mixture, the amount of solid phase is 22% by weight and the weight ratio between dimethyl sulfoxide and dichloromethylene is 110/90. Additionally, 2.6 mol of potassium hydroxide per 1 mol of biophenol A is used in this mixture, whereas MAX. Is used in an amount of 0.1 mol per 1 mol of biophenol A. As a result, I get a polyformal, characterized by a “1st intrinsic viscosity of 0.548 DL / g in chloroform at 25 ° C. The polymer consists practically of chemically bound biofiol A and formaldehyde groups. A strong elastic film is obtained by melting under pressure (compression) using the procedure described in Example 1 or by melting from a solution of chloroform. Example 3. A mixture consisting of chlorobenzene, dichloromethylene, potassium hydroxide granules, biophenol A, tetrabutylammonium bromide and 1.9 weight of water is subjected to stirring for 40 minutes. This mixture is characterized by a solids content of 19% by weight when chlorobenzene is used in an amount of 3 parts per 1 part of dichloromethylene and when using about 2.6 mol of potassium hydroxide per 1 mol of bisphenol A Additionally tetrabutylammonium bromide is present in the mixture in the amount of pores for 0.1 mol of a phase transfer catalyst per 1 mol of biophenol A. The result is a polyformal with a yield of 36%, characterized by a viscosity of 0.519 dl / g in chloroform at 25 ° C and consisting essentially of chemically bound groups of biophenol A and ormaldegida. A strong elastic film is produced by melting or pressure molding a polymer using the technique described above. Example 4. Mixture consisting of N-methylpyrrolidone, dichloromethylene,. potassium hydroxide granules and biophenol Ai were mixed for 30 minutes under almost anhydrous conditions. N-Methylpyrrolidone and dichloromethylene are used in equal weight parts of a polymer mixture characterized by a solid phase content of about 19 weight. This mixture also has a molar ratio between potassium hydroxide and biophenol A of 2.6 mol per mol. The resulting polyformal consists of chemically bound groups of biophenol A and formaldehyde, characterized by its own viscosity of 0.5 dl / g. A strong elastic film is made from polyformal using the melting methods described above or molded and compressed. Example 5. The procedure of Example 4 is repeated, except that instead of potassium hydroxide, use 2.1 mol of sodium hydroxide per mol of biophenol A. After about 1 hour, a polyformal is obtained (with a yield of .66%), characterized by intrinsic viscosity, about 0.80 dl / g. . Example 6. The procedure of Example 4 is repeated, except that 1 wt.% P-tro-t-butylphenol is used in the mixture, relative to the weight of biophenol A in the mixture, the mixture thus obtained is heated at 70 s. 105 min. In this example, the phase transfer catalyst is not used. As a result, a polyformal is obtained, characterized by intrinsic viscosity, O, 352 dl / g in chloroform with and consisting of practically bound high-pressure groups of biophenol A and formaldehyde. Chain growth is stopped with p-tert-butylphenol. There are groups of this compound at the ends of the chain. The resulting polyformal is melted or molded-melt under pressure (compression) to produce a durable elastic film. The above procedure is repeated, except that 2% by weight of the agent forming the reaction chain is used in the mixture subjected to the polycondensation reaction. It has been found that the intrinsic viscosity of the polyformal has decreased to 0.273. Next, the polycondensation reaction is carried out without the use of an agent that terminates the reaction using stoichiometric amounts of potassium hydroxide and biophenol A. It has been established that even if the mixture is heated and stirred for 2 hours at 70 ° C, the intrinsic viscosity of the resulting polyformal is 0.227 dl / year The low viscosity of the polyformal indicates that even in the case of K (when the polycondensation reaction mixture does not contain an agent that terminates the reaction chain and is heated for 2 hours, more than a stoichiometric amount of potassium hydroxide is needed to obtain a polyformal, characterized by intrinsic viscosity of at least 0., 3 dl / g Example 7. The reaction mixture consisting of dibromethylene, potassium hydroxide granules, bibphenol A and the MAX phase transfer catalyst is heated for 10 minutes. The mixture consisting of 11% by weight of the solid phase of potassium hydroxide is used in amounts corresponding to 4 mol of potassium hydroxide per 1 mol of biophenol A, while the catalyst The phase transfer is used in an amount of 0.1 mol of catalyst per 1 mol of biophenol A. As a result, a polyformal is obtained, consisting practically of chemically bound biophenol A and formaldehyde and characterized by intrinsic viscosity in chloroform at 25 ° C, equal to 1.9. The polymer is melted or molded under pressure (compression) to produce a durable elastic film. Example 8. A reaction mixture consisting of dibromomethylene 1,1-dichloro 2, 2-bis- (4-hydroxyphenyl) ethylene, potassium hydroxide granules and a phase transfer catalyst is subjected to heating and stirring for 75 minutes in almost anhydrous conditions The result is a polyformal consisting of practically formaldehyde particles chemically bound to particles characterized by the formula
    0group formaldehyde n groups characterized by the formula SG:. | | and intrinsic viscosity of 0.551 dl / g. This polymer is easily converted into a pro-elastic film by melting from a solution of chloroform or by casting under pressure (under compression). The glass transition point temperature is 115.0. . ; The film obtained in this way has valuable dielectric properties and is flame retardant, which makes it suitable for use as an anti-burning agent in production, by extrusion. pour, various plastics. The oxygen index of the film is 37.. . . Example 9. A mixture consisting of 16 parts (0.05 mol) 2,2-bis (p-hydroxyphenyl) -1,1,1 trichloroethane, 11 parts (0.195 mol) of KOH granules, 56 parts of dibrrmmethylene and 66 parts N-methylpyrrolodone is subjected to stirring when refluxing (at). Thirteen minutes later they observe mine; The intensive exothermic reaction and the viscosity of the reaction mixture increase. After 51 minutes, the reaction mixture is taken up in methanol and the polymer is separated in the usual way. The result is a polyformal with a yield of 75%, consisting practically of formaldehyde groups, chemically bound to groups characterized by the formula and intrinsic viscosity of 0.745 dl / g. Example 10. A mixture consisting of methylene chloride, N-methylpyrrolido granules of potassium hydroxide and 9,9-bis- (4-hydroxyphenyl) -fluusrene is subjected to stirring for 6 minutes at 70 ° C in almost anhydrous conditions. The result is a polyformal, characterized by a viscosity of 0.638 dl / g, consisting essentially of chemically bound. The result is a polyformal with a yield of 63%, from which a strong elastic film is produced by melting or forming under pressure; The product has a glass transition temperature of 221 ° C. Example 11 :; A mixture consisting of 2.3 parts (0.01 mol) and biophenol A, 1.7 parts (0.026 mol), 85% powdered potassium hydroxide, 0.47 parts (about, 001 mol) MAX and 53 parts of dichloromethylene is subjected to stirring at room temperature for 18 hours under almost anhydrous conditions. This reaction mixture is then washed with water until it becomes neutral. Further methanol is added to the reaction mixture, which results in the product precipitating out. In this case, the yield of polyformal reaches 49%. P formalformal has a intrinsic viscosity of 0.31 dl / g and consists of practically chemically bound groups, biophenol A and formaldehyde. Prib (1р 12. The mixture is agitated in a closed system with. The mixture consists of 3600 parts of dichloromethylene, 119 parts (0.238 mol) MAX, 542 parts (2.37 mol) of biophenol A and 400 parts (6.2 mol) of potassium hydroxide granules The mixture thus obtained is subjected to stirring for 115 minutes. As a result, a polyformal is obtained, consisting essentially of chemically bound particles of biophenol A and formaldehyde, characterized by a specific viscosity of 0.551 dl / g. spu of dichloromethylene, N-methylpyrrolidone, potassium hydroxide granules and 2, 2-bis- (4-hydroxyphenyl) -butane, is stirred at 70 ° C for 30 minutes under almost anhydrous conditions.This mixture has a solids content of 15%, dichloromethylene is used in an amount of 52 parts per 60 parts of N-methylpyrrolidone, and the amount of potassium hydroxide corresponded to 2.6 mol per 1 mol of 2.2-bis- (4-hydroxyphenyl) -butane. As a result, a polyformal is obtained, consisting essentially of chemically
    Example 16. A mixture consisting of dichloromethylene, chlorobenzene, graSample 19. A mixture consisting of 30 parts. 0.1 mol 3,4-bis- (p65
    -oxiphenyl) -3,4-toxanidol, 14.6 parts (0.25 mol) of rfiSfiyjt KOH, 81 parts of dichloromethylene and 93 parts of N-methylpyrrodone, are mixed and heated to reflux (). After 81 minutes, another 11 parts (0.2 mol) of KOH GRANUL were added. After 92 minutes, the very thick reaction mixture is drunk into methanol in order to recover the polymer. The result is a polyformal suitable for making a film and consisting of formaldehyde particles chemically bound to particles characterized by the structural formula of the form
    The resulting polymer has an intrinsic viscosity of 0.564 dl / g and a glass transition temperature of 679s.
    776564
    12
    Although N-methylpyrrolidone is used to obtain the above polyformal, the invention allows the use of a wide range of dipolar. Proton solvents, which are used to prepare a polyformal reaction mixture at 25%, and in amounts of 5-95% relative to the total weight of the mixture.
    Thus, the proposed 1 st method allows to obtain aromatic polyformals with an increased molecular weight.
    权利要求:
    Claims (1)
    [1]
    1. Patented Mr. Sha 3069386, cl. 260-49, publ. 1 $ 60 (prototype).
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US73956276A| true| 1976-11-08|1976-11-08|
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