Patent GB-866401-A (GB)
Title: Heat-sensitisation of latices
IPC: C08C1/14
Filed: 1958-10-14
Abstract: Latices of high polymers are rendered heatsensitive by incorporating water-soluble compounds having two or more acetal groups.  Latices of natural rubber and of rubber-like polymers of butadiene, dimethylbutadiene and isoprene, copolymers of butadiene, dimethylbutadiene and isoprene with styrene, a -methyl styrene, acrylonitrile, methacrylonitrile, acrylates and methacrylates, polymers of chlorobutadiene, copolymers of chlorobutadiene with mono- or di-olefines, and copolymers of isoolefines such as isobutylene with small amounts of conjugated diolefines are referred to.  The polyacetals are preferably of molecular weight 400-50,000 and may be made by reacting an aldehyde with a dihydric alcohol, possibly in the presence of a monohydric alcohol or a trior higher polyhydric alcohol.  The polyacetals made in the absence of these last mentioned alcohols may be acetalized or re-acetalized with them.  The terminal hydroxy groups of the polyacetals may be etherified or reacted with an acid anhydride (e.g. acetic or propionic anhydride), an acid chloride (e.g. benzoyl chloride), phenyl or stearyl isocyanate, or a compound having a double bond (e.g. acrylonitrile, vinyl ethyl sulphone or vinyl methyl ketone. Example 1 is concerned with heat-sensitizing batches of a mix of 60% concentrated rubber latex, zinc oxide, sulphur, zinc diethyl dithiocarbamate, methylenebis (sodium naphthalene sulphonic acid), hydroxyethylated polycyclic phenol and formaldehyde by 15% aqueous solutions of polyacetals obtained from (1) butane-diol -1, 4-di(hydroxyethyl ether) and paraformaldehyde; (2) butanediol- 1, 4-di (hydroxyethyl ether), triethylene glycol and paraformaldehyde; (3) butane-diol-1, 4-di (hydroxyethyl ether), octaethylene glycol and paraformaldehyde, or (4) butane-diol-1, 4-di(hydroxyethyl ether), dodecaethylene glycol and paraformaldehyde.  Example 2 is concerned with heat-sensitizing batches of a mix, of pH 9,5, of 50% polychlorobutadiene latex, p zinc oxide, sulphur, zinc diethyldithiocarbamate, methylene-bis (sodium naphthalene sulphonic acid), hydroxyethylate polycyclic phenol and aminoacetic acid by 15% aqueous solutions of polyacetals obtained from (1) triethylene glycol, thiodiglycol and paraformaldehyde; (2) butane-1, 3-diol-dihydroxyethyl glycol and paraformaldehyde; (3) triethylene glycol, hexane-1, 6-diol and paraformaldehyde; (4) butane dihydroxyethyl glycol, dodecanol and formaldehyde; (5) dipropylene glycol, triethylene glycol and formaldehyde, or (6) tripropylene glycol and formaldehyde. Example 3 is concerned with heatsensitizing batches of a mix, of pH 7,5, of 40% butadiene-styrene copolymer latex, mineral acid, methylene-bis (sodium naphthalene sulphonic acid), zinc oxide, sulphur, and zinc dibutyl dithiocarbamate by 15% aqueous solutions of the polyacetals of Examples 1 and 2.  Example 4 is concerned with heat-sensitizing batches of a mix of a 50% butadiene-acrylonitrile copolymer latex, methylene-bis (sodium naphthalene sulphonic acid), zinc oxide, sulphur, 2-mercaptobenzthiazole and diphenylguanidine by 15-30% aqueous solutions of the polyacetals of Examples 1 and 2.  Example 5 is concerned with heatsensitizing 45% polyvinyl acetate, 40% polyacrylic acid methyl ester and 50% polyvinyl chloride dispersions with 15% aqueous solutions of the polyacetals of Examples 1 and 2.ALSO:Water-soluble compounds having two or more acetal groups for use in rendering heatsensitive the latices of high polymers (see Group IV(a)) may be prepared by condensing an aldehyde e.g. paraformaldehyde or aqueous formaldehyde with a glycol or hydroxylated glycol in the presence of a catalyst, e.g. para toluene sulphonic, hydrochloric, phosphoric or trichloracetic acid, zinc chloride or potassium bisulphate, or may be prepared by the polyaddition of glycols to divinyl ethers of glycols. Examples of the glycols used are: ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tetrapropylene glycol, butanediol, pentanediol, hexanediol, octanediol, thiodiglycol, and substitution products of these such as the alkyl and aryl compounds and hydroxylation products, e.g. reaction products of the glycols with ethylene oxide, propylene oxide, isobutylene oxide, cyclohexene oxide and styrene oxide. Preparation of the polyacetals may be in the presence of mono- or higher hydric alcohols, e.g. methyl, ethyl, butyl and benzyl alcohols, trimethyl propane, glycerol, butanetriol, thiopentaerythritol, or a hydroxyalkylation product of such an alcohol.  The polyacetals prepared without the addition of such alcohol may be reacted with the alcohol to acetalize or reacetalize. The hydroxy groups of the hydroxyacetals may be esterified or etherified by reaction with acid anhydrides or chlorides or reacted with phenyl or stearyl isocyanate, or may be united with double-bond compounds such as acrylonitrile, vinyl ethyl sulphone or vinyl methyl ketone.  Polyacetals of glycols and hydroxyalkylated glycols having at least one oxygen atom to four carbon atoms are preferred.  The polyacetals are preferably of mol. wt. 400-50,000, e.g. 10,000.