DE1218727B - Molded parts made from condensation products of diphenyl oxide - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

C 08g

German class: 39 b -22/10

Number: 1218 727

File number: D 38979 IV c / 39 b

Filing date: May 23, 1962

Opening day: June 8, 1966

The subject of the invention is a process for the production of molded parts by heat curing molding compounds, the

a) Condensation products of at least two halomethyl groups containing diphenyloxyds with a hydroxyl-substituted aromatic compound, the at least two labile Has nuclear hydrogen atoms in positions activated by the phenolic hydroxyl groups or condensation products of such a diphenyl oxide prepared in the presence of a base with a hydroxyl-substituted aromatic compound containing at least two hydroxyl groups contains,

b) formaldehyde, paraformaldehyde or hexamethylenetetramine and

c) optionally fillers

contain.

Of the first group of condensation products, i. H. those in which the hydrogen atom from the aromatic nucleus of the hydroxylated compound has been split out, those are preferred which fall under the general formula below.

HA-CH ₂ -B-CH ₂ - (- A-CH ₂ -B-CH ₂ ) -AH

(1)

In this formula, η denotes an integer from 1 to 6, A denotes the remainder of the hydroxylated aromatic compound, the ether bond leading to that aromatic nucleus which has one or more free hydroxyl groups, and B denotes the aromatic part of the halomethylated compound with the formula below :

(2)

These condensation products can expediently be prepared by one at increased Molded parts made from condensation products of diphenyl oxide

Applicant:

The Dow Chemical Company, Midland, Mich. (V. St. A.)

Representative:

Dipl.-Ing. F. Weickmann,

Dr.-Ing. A. Weickmann,

Dipl.-Ing. H. Weickmann

and Dipl.-Phys. Dr. K. Fincke, patent attorneys, Munich 27, Möhlstr. 22nd

Named as inventor:
Howard Paul Cordts, Bay City, Mich .; Alexander Michael Partansky, Concord, Calif. (V. St. A.)

Claimed priority:
V. St. ν. America May 29, 1961 (113 097, 113 096)

Temperature a hydroxylated aromatic compound with at least two labile nuclear hydrogen atoms can react with a halomethylated diphenyl oxide, the latter having at least two halomethyl groups having.

Within the second group of condensation products, those in which the hydroxyl group the hydroxylated compound formed an ether bond with the halomethyl group those with recurring groupings of the following general formula are considered to be preferred:

■ O - C - O - (- CH ₂ - B - CH ₂ - O - C - O -) - CH ₂ - B - CH ₂

In this formula, B denotes a group. These condensation products with the ether groups

According to the formula (2) and C is a radical which can also be obtained by 50 pings can be represented by the formula for B, which is a polyhydroxylated aromatic compound dihydroxylated compound. reacts with a halogenated diphenyloxide

609 578/595

can yaw, which contains at least two halogen groups, in the presence of a base, for example NaOH; if desired, a salt of the polyhydroxylated compounds with the halomethylated compounds can also be used Let connections react.

example 1

a) Manufacture of the polymer referred to here
no protection is claimed

352.5 g of phenol (3.75 moles) were heated to 70 ° C; 667.5 g (2.5 mol) of 4,4'-bis (chloromethylphenyl) oxide were dissolved in 612 g of toluene and added over a period of ¹ Z _{2 hours with stirring.} During the addition, the reaction mixture was kept at 70 to 80 ° C. by external cooling. Volatile reaction products were removed under vacuum; the final conditions were 180 to 182 ^° C at 2.5 cm Hg; the discharge of the volatile reaction products was continued for 30 minutes, and 790 g of a resinous material having a melting point of 90.5 ° C. and a chlorine content of 0.01% were obtained.

b) The method according to the invention

189.5 g of the product obtained in this way were placed in 600 g of toluene and 105 g of hexamethylenetetramine Addition of 200 g of sawdust dissolved. The mixture was in vacuum for 18 hours at 60-70 ° C dried. The dry powder was molded at 150 ° C. under a pressure of 336 atmospheres.

Comparative experiment

In addition, a commercially available phenol-formaldehyde resin with hexamethylenetetramine and

t5 sawdust mixed and deformed in the same way. The two resins were compared with one another by making test strips of 51 x 12.7 x 3.1 mm and immersed in a boiling normal sodium hydroxide solution.

ao The results of these comparative tests are shown in the table below.

No. Treatment
liquid Treatment time
in hours Weight
change
in% Changes in appearance and other comments 6A j
6B J n / l NaOH
n / l NaOH
n / l NaOH
n / l NaOH
n / l NaOH
n / l NaOH 4th
30th
96
4th
30th
96 + 59
+ 59
+ 73.7
+ 31
+ 30 Sample begins to swell; Very rough surface
severely swollen; Cracking
heavily torn and swollen, very dark ver
coloring
slight staining on the surface
slightly swollen; slight staining
slightly swollen, otherwise still in good condition

Identification of the sample:
6 A = phenol-formaldehyde resin.
6B = phenol-chloromethyldiphenyloxyd resin.

Example2

a) 69 g of chloromethylated diphenyl oxide with an average of two chloromethyl groups per diphenyl oxide group (0.25 mol) and 60 g of bisphenol-A (0.25 mol) were dissolved in 100 ml of dioxane and dissolved in placed in a three necked reaction flask; this was with a mechanical stirrer, a reflux condenser and a thermometer. The mixture was 22.5 g of sodium hydroxide dissolved in 50 ml of dioxane were added over the course of 5 minutes with stirring. After finishing the addition, that became The mixture was heated to 63 ° C. and held at this temperature for 2 hours. The reaction mixture was then cooled to room temperature and washed with warm water until the entire Sodium chloride was removed. The resulting white powder was filtered and removed Water dried. Analysis revealed no phenolic hydroxide groups, p-substitution and absence of chloromethyl groups.

b) The product according to Example 2 became a fine powder ground, mixed with 10 weight percent hexamethylenetetramine and brought into a mold. The material was then treated at 200 ° C. and 25.5 atmospheres. The end product was a clear, transparent one Plate won.

Claims (1)

Claim: Process for the production of molded parts by thermosetting molding compositions which a) Condensation products of a diphenyl oxide containing at least two halomethyl groups with a hydroxyl-substituted aromatic compound that has at least two labile nuclear hydrogen atoms in through the phenolic Has hydroxyl groups activated positions or in the presence of a base produced condensation products of such Diphenyloxyds with a hydroxyl-substituted aromatic compound, which at least contains two hydroxyl groups, b) formaldehyde, paraformaldehyde or hexamethylenetetramine and c) optionally fillers
contain. 609 578/595 5.66 © Bundesdruckerei Berlin