Patent GB-441064-A (GB)
Title: Improvements in the manufacture and production of polymerisation products
IPC: C08F16/12
Filed: 1934-07-09
Abstract: Solid elastic rubber-like masses are manufactured by polymerizing vinyl isobutyl ether of a high degree of purity, or mixtures thereof with other polymerizable substances, e.g. other vinyl ethers or isobutylene, at temperatures below 10 DEG  C., e.g. - 80 to 0 DEG C., preferably about -40 DEG  C., by means of boron fluoride, as such or in the form of its addition products with organic oxygen bearing compounds, e.g. ethers such as diethyl or dibutyl ether, ketones or alcohols, in the presence or absence of diluents.  The polymerization is advantageously carried out in the presence of liquid ethane or propane or organic solvents to which solid carbon dioxide has been added, or with the addition of carbon dioxide alone.  The products may be employed as electric insulating materials, as coating agents, caulking compositions or adhesives or for the manufacture of shaped articles.  Solutions of the products may be used to provide solid substances such as metals, wood, textiles, paper, films or articles of nitrocellulose or acetyl cellulose with coatings or impregnations which are resistant to weathering, acid vapours and caustic alkalies. Films from the products are useful for the preparation of waterproof and unbreakable fabrics by introducing the films between strips of fabric and pressing while heating.  There may be added to the products rubber, resins, synthetic polymerization products, e.g. of diolefines such as butadiene, chlorodiolefines, acrylic acid compounds, organic and inorganic vinyl esters, vinyl ketones and styrene, softening agents, e.g. stearic acid, fillers, e.g. carbon black, kaolin, cork meal, or dyestuffs.  When the added substances are capable of vulcanization, the coatings or impregnations may be p vulcanized.  The polymerization products are also suitable as combining layers in the production of non-splintering glass, by inserting a film of the product, if desired, swollen with solvents, between two glass sheets and pressing the whole together, or by spreading the still sticky polymerization products on a sheet of glass and pressing on a second sheet, or by employing films of nitrocellulose or acetylcellulose coated with still sticky polymerization products, or by producing a film of liquid monomeric vinyl isobutyl ether or of a liquid polymerization product of a low degree of polymerization on a sheet of glass and pressing on a second sheet which has been exposed to the action of gaseous boron fluoride, whereby polymerization is effected between the sheets.  Additional substances such as softening agents or dyestuffs may be incorporated in the polymerized or monomeric vinyl isobutyl ether.  In examples: (1) vinyl isobutyl ether is fractionally distilled three times over powdered potassium hydroxide, then twice fractionally distilled and allowed to stand over sodium wire after each distillation, and finally again distilled; the purified substance is mixed with liquid propane and gaseous boron fluoride is led in; (2) vinyl isobutyl ether, purified as in (1), is made into a paste with solid carbon dioxide and treated with gaseous boron fluoride; (3) a mixture of vinyl isobutyl ether and liquid propane is supplied to a mixer together with liquid propane saturated with boron fluoride; (4) sheet aluminium is coated by immersion in a solution of the product of (1) in benzene; (5) a film of the product of (2) is placed between two sheets of fabric, e.g. of cotton, wool, linen, silk or artificial silk, and the whole is pressed while heating; alternatively, a sheet of fabric is coated on one side by pressing a film of polymerization product between the fabric and a film of cellulose which is subsequently removed; fabrics, paper or leather may be impregnated by drawing them through a solution of the polymerization product in benzine; (6) stuffing for cushions, e.g. horsehair, kapok or seaweed, is sprayed with a solution of the product of (1) in ether, whereby the fibres are stuck together; pressed materials and leather fibres may be similarly stuck together; (7) a film of acetyl cellulose, nitrocellulose or cellulose is provided on both sides with a film of the product of (1), a layer of fabric is applied on both sides and the whole is pressed while heating; (8) a film of the product of (1) is pressed between two sheets of glass; the glass sheets or the film may be previously coated with softeners, e.g. organic solvents, or substances which increase the adherence of the film, e.g. polymerized isobutylene; (9) monomeric vinyl isobutyl ether, if desired with the addition of substances which increase its viscosity, e.g. polymerization products of other vinyl ethers or of isobutylene, is poured over a sheet of glass and a second sheet which has been exposed to boron fluoride or an addition product thereof, e.g. with ether, is pressed thereon; (10) films are cast from a solution of polymerized vinyl isobutyl ether on two glass sheets provided with borders, which are then warmed to dry the films and pressed together. Specification 378,544 is referred to.