DE1233598B - Process for the production of crosslinked polyesters - Google Patents

Description

GERMAN

PATENT OFFICE

EDITORIAL

German class 39 c-16

Number: 1 233 598

File number G 25151IV di39 c

Registration date: 21 August 19

Opening day 2 February 1907

There is already a method of making Alkyd resins have become known, in which em ester condensation product produced from citric acid and glycols hardened by adding aldehydes or aldehyde-releasing substances in the heat will. Reactive hydroxyl groups are still present in the ester condensation product react with the aldehyde, thereby hardening the product.

It is also known that polyesters containing reactive groups with HiKe an aldehyde The separating compound is hardened, i.e. it can be networked

The invention now relates to a process for the production of crosslinked polyester by heating a mixture of polyester and aldehyde or an aldehyde-releasing compound, which is characterized in that a mixture of a polycarbonate, the carbonate residues of which are directly bound to aromatic po age, and 0, 5 to 30 weight percent, based on the polycarbonate portion, hexamethylenetetramine or paraformaldehyde to temperatures of 100 heated to 300 ⁰ C.

Unexpectedly, it has been found that polycarbonates, which do not have reactive groups, can be crosslinked by the process of the invention. Linear polycarbonates are known. They have good physical, chemical and electrical properties, but are easily soluble in many organic solvents Use is restricted Polycarbonates can be produced in a known manner using bifunctional phenol compounds (see "Angewandte Chemie", 1956, p. 633 and f)

To produce the polycarbonates used by the process of the invention, bifunctional phenolic compounds can be used which contain one or more aromatic rings and in which the hydroxyl groups are directly bonded to aromatic rings. For example, 2,2-bis- (4-oxyphenyl) -propane (bisphenol-A), 2,4'-dioxydipbenylmethane, bis- (2-oxyphenyl) -methane are suitable; Bis (4-oxyphenyl) methane, bis (4-oxy-5-rutrophenyl) methane; Bis (4-oxy-2,6-dimethyl-3-methoxyphenyl) methane, l, l-bis (4-oxyphenyl) ethane, 1,2-bis (4-oxyphenyl) ethane, l, l-bis (4-oxy-2-chlorophenyl> ethane, 1,1 - bis - (2,5 - dimethyl -A- oxyphenyl) - ethane, 1,3 - bis - (3 - methyl - 4 - oxyphenyl) propane, 2,2 - bis (3-phenyl-4-oxyphenyl) propane, 2,2-bis (3-isopropyl-4-oxyphenyl) propane, 2,2 - bis - (3 - isopropyl-4-oxyphenyl) -propane, 2,2-bis- (4-oxynaphthyl) -propane, 2,2-bis- (4-oxyphenyl) -pentane, 3,3-bis- (4-oxyphenyl) -Process for Manufacture of cross-linked polyester

Applicant

General Electric Company,

Schenectady, N Y (V St A)

representative

Dipl.-Ing M Licht and Dr R Sbhmidt, Patent Attorneys, Munich 2, Theiesienstr 33

Named as the inventor
Kenneth Bernard Goldblum,
Pittsfield, Mass. (V St A)

Claimed priority.

V St ν America from 22 Augusi

1957 (679740)

pentane, 2,2-bis (4-oxyphenyl) -hep phenyl) -phenylmethane, bis- (4-oxyphenyl) -l, 2-bi 2,2-bis (4-oxyphenyl) -1,3-bis (pheD 2,2-bis- (4-oxyphenyl) -l-phenylpropai

an, bis- (4-oxyenyl) -cyclohexyl- »- (phenyl) -athane,

Dioxybenzenes can be used, such as hydroquinone and resorcinol, and dioxydiphenyls, diphenyl, 2,2'-dioxydiphenyl, 2,4 ' Dioxynaphtha faucets such as 2,6-dioxyn; Dioxyarylsulfones can be used, phenyl) sulfone, 2,4'-dioxydiphenyls

2,4 '- dioxydiphenylsulfone and 3' - C bloi - 4,4 '- dioxyphenylsulfone Also aromatic dioxyather are

suitable, such as B. 4,4'-dioxydiphen 4,2'-, 3,3'-, 2,2'- and 2,3'-dioxydipherals oxy-2,5-dimethyldiphenyl ether, 4,4 methyldiphenyl ether, 4,4'-dioxy-3

I) -propane or likewise can

such as 4,4'-dioxy- -dioxydiphenyl, phthahn Also ζ Β Bis- (4-oxyilfon; 5'-chlorine

lather, the 4,3'-, ylather, 4,4'-di- - Dioxy-2,6-di- - dusobutyldiphenylether, 4,4'-Dioxy-3,3-dusopropyldiphenylether, 4,4'-dioxy-3,2'-dimtiodiphenylathc 3,3'-dichlorodiphenyl ether; 4,4'-Diox phenyl ether, 4,4 '- Dioxy - 2,3' - dibro ndiphenyl ether,

4,4 '- Dioxydmaphthylather, 4,4' - Dio dinaphthyl ether, 4,4'-dioxy-2j6-dimethyldiphenyl ether and 4,4'-dioxy-2,5-dietoxydipienyl ether

The polycarbonates used according to the invention can ζ Β in a known manner by transesterification at temperatures between 150 and 3 (pressure from 0.01 to 5 to 10 mm iQue < can be used for the transesterification conventional catalysts used w

4,4'-Dioxy- -3,3'-difluorodi-

: y-3,3'-dichloro-

10 ° C and a ksilver received

earth for the

709 507/407

Claims (56)

3 4 Diaryl carbonates are used for transesterification. The product was insoluble in dioxane, making Games for the diaryl carbonates are symmetrical as the cross-linking is shown Carbonates, such as diphenyl carbonate, di-fhalophenyl) - ", _," carbonate, ζ B di- (chlorophenyl) carbonate, di- production of polycarbonate B (bromophenyl) carbonate, di- (polyhalophenyl) -carbo- 5 The polycarbonate was prepared as according to A, nate, ζ B di- (trichlorophenyl) carbonate or di- (tn- that is, 0.3 mol of bisphenol-A and bromophenyl) carbonate, di (alkylphenyl) carbonate, 0.33 mol (10% excess) diphenyl carbonate and ζ B Di- (tolyl) carbonate, di (naphthyl) carbonate, it boiled in vacuo after pheno-destillation Di- (chloronaphthyl) carbonate, asymmetrical carbonate, the constituents were under pressure for 4 hours nate, e.g. B. Phenyl-tolyl-carbonate, chlorophenyl-chloro- io boiled from 0.2 mm of mercury. _H naphthyl carbonate and trichlorophenyl chlorotolyl _, " carbonate example, game 2 Preferably, those used according to the invention are used. Approximately 0.5 g of polycarbonate B were 0.1 g deten polycarbonates mixed using phosgene hexamethylenetetramine and placed on a heating m an organic basic substance, such as ζ B tertiary 15 plate ^{heated to about 180 0} C after about 5 minutes Amines (e.g. Pyndine, Dimethylanilm or Quinolm), beating with the spatula transformed the mixture The base can be used undiluted or diluted in a yellow, rubbery, non-melting mass, m neutral solvents, ζ B. hydrocarbons, which indicated a cross-linking. Pieces of the same such as benzene, toluene or xylene, or alkyl halides, resin without the addition of hexamethylenetetramine such as chloroform or methylene chloride, used 20 were beaten, did not change their appearance, Tertiary wet nurses are advantageous in that the cross-linked resin was insoluble in dioxane. they act as catalysts in the reaction, good _IT ", _,, _ Represent solvents and the hydrogen halide production of the polycarbonate C Acid, which is given off during the reaction, is collected in a mixture of 135 kg Pyndin, 13.5 kg The reaction is preferably carried out at temperatures of 25 bisphenol A and 28 g of phenol, phosgene was em- between 25 and 5O ⁰ C carried out in place of routed, allowed to 5.4 kg per hour with stirring Phosgene itself can e.g. B dibromine and diiodine bubbled through the solution and led at a temperature carbonyl as well as bis-halogenfonmate the two-door from 25 to 35 ° C 1 hour and 12 minutes this Valuable phenols (e.g. bis-chlorforimate from hydro-process by at this moment were chmon or bisphenol-A) or glycols (e.g. bis- 30 1.35 kg phenol dissolved in pyndm of the stirred chlorfonmate of the ethylene glycol, the neopentyl reaction mixture added the polycarbonate glycol or polyethylene glycol) was used only isopropanol and precipitated twice In the method of the invention, the washouts are washed and centrifuged after each ingredients mixed in the dry state, and the mixture filtered. Mixture is brought to a temperature between 100 and 35. 300 ° C, with temperatures between 150 and B e 1 s ρ 1 e 1 3 250 ⁰ C are the most favorable various mixtures of the polycarbonate C The following examples are intended to illustrate the process of using additives of 0.5 to 20 percent by weight Describe the invention in more detail. Hexamethylenetetramine produced the mixtures ". ",, ^. 40 were dissolved in chloroform and samples of the solution Production of the polycarbonate A _{m A} i _ummramg efaße given and brought to room temperature 68.4 g (0.3 mole) bisphenol-A and 64.2 g (0.3 mole) held door until the solvent had evaporated. The diphenyl carbonate samples were then placed in a hot-air oven heated to 230 ° C, with a stirrer placed at certain distances, an inlet opening for an inert gas and a 45 m and for their solubility in paradioxane checked. Cooling system was equipped, which was an evacuating contained The sample with 0.5% hexamethylene tetramine connected device Slowly was some insoluble material after 16 hours introduced nitrogen in the system was gradually stood at 230 ⁰ C in an oven evacuated samples with more The distillation of the phenol as 1 percent by weight of hexamethylenetetramine released em when the temperature of the bath after about 50 held after 6 hours in the oven some insoluble Va hour heating reached about 185 to 19O ⁰ C and material. Samples with 5% or more hexamethylene set themselves up quickly at this temperature and a tetramine showed a further 1.1 to 1V ₂ hours of insoluble material after only 30 minutes of hot pressure of 10 mm of mercury. After this time, the largest part of the phenol produced according to the invention crosslinked poly was distilled off. The temperature of the ester can be used to isolate wires. They are also increased in the form of molding powder aEein 9 to 12 mm of mercury slowly to 290 ⁰ C, or in conjunction with fillers for producing and held about 4.5 hours at this height. suitable for molded parts. The viscosity of the adjustable products increased during this time according to the invention and are also very valuable reaction mixtures. 60 plastic glue. ^Beis P ^{iel J} patent claim
To 0.5 g of the polycarbonate A prepared as above 0.1 g of hexamethylenetetramine were used on a heating process to produce crosslinked polyesters plate of about 180 ° C added The starting materials 65 by heating a mixture of polyester and were mixed and beaten with a spatula, aldehyde or an aldehyde-releasing compound and after 30 seconds there was a yellow, rubbery, manure, characterized in that A non-melting, cold-break product resulted in a mixture of a polycarbonate whose Smd carbonate radicals bonded directly to aromatic Rrage, and heated for 0.5 to 30 weight percent, based on the polycarbonate portion, hexamethylenetetramine or paraformaldehyde at temperatures of 100 to 300 ⁰ C. Considered Dm German Patent Specifications No. Swedish Patent No. 133,339; Angewandte Chemie, Vol. 68 (l! When the registration was announced, a voucher was displayed. label: 712002, 305 775; 56), S 633 to 640.