The way to obtain a latex of a copolymer of vinylidenechloride
(57) Abstract:Usage: in the field of polymer technology, namely how to obtain latexes of copolymers of vinylidenechloride used in the manufacture of latex paints, polymer compositions. The inventive process copolymerization VDH with vinyl chloride and unsaturated carboxylic acid is carried out in the presence of a mixture of emulsifiers, one of which is alkylphosphonate sodium with the number of carbon atoms in the alkyl 12-18, and as another emulsifier used ammonium salt of sulfonated 15-20 wt. % alkylperoxo ether of polyethylene glycol with a number of carbon atoms in the alkyl 8-12 and the number of hydroxyethyl groups 10-12 in number in a mixture of emulsifiers 65-75 wt. % when the content of the emulsifier mixture of 3,5-5,0 by weight of comonomers. table 1. The invention relates to the field of polymer technology, namely a process for the production of latexes of copolymers of vinylidenechloride (VDH), used in the manufacture of latex paints (VDK), polymer compositions may be used to produce frost-resistant latex copolymers VDH with vinyl chloride (I) unsaturated carboxylic acid (maleic, f is lastnosti, due to the unique combination of several of their properties: high water, acid and alkali, non-combustible, odorless, resistant to organic solvents, mineral oils.Increasing the frost resistance of latex used for these purposes is the actual problem, the solution of which can significantly reduce the cost of transporting and storing them in the winter.For aqueous dispersions of copolymers produced as a commercial product, an important property is also aggregate stability, because many consumers have high requirements for the retention of latex, which must be not less than three months. In addition, aggregate stability required for transportation of latex over long distances.It is known that the incorporation in the copolymer VDH RIN unsaturated carboxylic acids such as methacrylic, acrylic or maleic increases the frost resistance of latex. However, the resistance of these latexes does not meet the requirements of use, for example, VDK (at least 5 cycles of freezing at minus 40oC for 6 hours and thawing at 20-25oC for 18 h) and accounted for the receipt of high-concentration aleksov copolymers VDH with I  by copolymerization VDH with I in aqueous emulsion in the presence of a water-soluble initiator and an emulsifying system, consisting of alcohol and ionic emulsifier, and as an alcohol, a mixture of fatty alcohols with an unbranched chain WITH14-C16or17-C180,5-0,8 wt.h. and as an emulsifier alkylphosphonate sodium12-C18in the alkyl, at a ratio of components of the emulsifying system 1:3-1:5, respectively, in a process carried out at a dosage VDH and a mixture of fatty alcohols WITH14-C16or17-C18during copolymerization. Get the latex with the following mechanical properties: stability during storage is more than 6 months, the dry matter content of more than 60 wt. the surface tension of 35 to 40 mn/m, pH 7.0 to 8.0, but latex does not have frost (see table, example N 16). Introduction in the polymerization recipe of 1.5 wt.h. unsaturated carboxylic acids (maleic, fumaric or takenaway) only slightly improves the frost resistance of latex of a copolymer based on VDH (1-2 cycles).The technical result of the invention is to increase the frost resistance of latex copolymer VDH with I and unsaturated carboxylic acid.The result is achieved that the method of obtaining LVII water-soluble initiator and a mixture of emulsifiers, containing alkylphosphonate sodium with the number of carbon atoms in the alkyl radical of 12-18, with dosage VDH and mixtures of emulsifiers in the course of polymerization, the mixture of emulsifiers contains 65-75 wt. ammonium salts of sulfonated 15-20 wt. alkylphenolates ether of polyethylene glycol with a number of carbon atoms in the alkyl radical 8-12 and the number of hydroxyethyl groups of 10-12 when the concentration of the mixture of emulsifiers is 3.5 to 5.0% by weight of comonomers.The essence of the invention is illustrated by the following examples.Example 1 (invention).In a reactor with a volume of 4 l and load (wt.h.) 92 demineralized water, 1,5 maleic acid, 0,6 alkylphosphonate sodium 1,4 ammonium salts of sulfonated 15 wt. alkylperoxo ether of polyethylene glycol with a number of carbon atoms in the alkyl 8-12 and the number of hydroxyethyl groups 10-12 (emulsifier S-10, THE 6-02-09-13-87), 0.6 ammonium persulfate, 19 VDH and 34 I, with stirring, the reaction mixture is heated to 50oC and carry out the copolymerization at a constant temperature. Through 1 h after reaching the set temperature start to dose in the reactor 45,5 VDH and the mixture (solution) of 0.6 alkylphosphonate sodium, 1.4 emulsifier With 10 and 8 of demineralized water. With the ATM. After stavki monomers latex Tegaserod vacuum when the vacuum 700-720 mm RT.article and temperature 55oC for 1 h If the concentration of residual monomers not reduced below 0.03 wt. I and 0.01 wt. VDH, the operation of the degassing continued for 0.5-1 hours After degassing the reactor through latex miss gaseous ammonia to pH 7.0, then gradually add 2.0 to 2.5 wt. including crystalline NH4HCO3, after which the pH of the latex is raised to 8.0. Get a latex of a copolymer with the content, wt. VDH 64-66, I 32-35, unsaturated carboxylic acid 1-2.Frost latex define in the chamber with a temperature of minus 40oC. the Latex in the amount of 100-125 ml is placed in a jar of tinplate volume of 250 ml (diameter 70-75 mm, height 65 mm) and incubated in a chamber at minus 40oC for 6 hours defrosting the latex occurs at 20-25oC for 18 h After thawing few ml of latex was poured on a glass plate (or Petri dish), and then tilt it at 45ofor draining excess latex. Latex believe stands the test, if the latex film on the glass is homogeneous.Stability in storage is determined by observation of the sample latexes) and visually the presence of coagulum in the form of sediment at the bottom of the flask.The dry residue is determined by drying in a heating Cabinet at a temperature of 755oC to constant weight; the surface tension according to the method of Du-Nui, pH at pH meters type LPU or monomer EV-74.The process conditions copolymerization VDH with I and unsaturated carboxylic acid and the properties of the obtained latex of the copolymer are shown in table.Examples 2-15 (invention), examples 17-23 (for comparison) carried out as in example 1. Conditions of the copolymerization process and properties of the obtained latexes of copolymers are shown in table. The way to obtain a latex of a copolymer of vinylidenechloride by copolymerization of vinylidenechloride, vinyl chloride and an unsaturated carboxylic acid in an aqueous medium in the presence of a water-soluble initiator and a mixture of emulsifiers containing alkylphosphonate sodium with the number of carbon atoms in the alkyl radical of 12 to 18, with a dosage of vinylidenechloride and mixtures of emulsifiers in the course of polymerization, characterized in that the mixture of emulsifiers contains 65-75 wt. ammonium salts of sulfonated 15 -20 wt. alkylperoxo ether of polyethylene glycol with a number of carbon atoms in the alkyl radical of 8 to 12 and the number of hydroxyethyl groups 10 12 when the concentration of the
FIELD: polymer production.
SUBSTANCE: invention relates to the field of production of thermoplastic polymer materials, in particular vinylidene chloride/vinyl chloride copolymers, suitable for manufacturing technical-destination articles. Method is accomplished by copolymerization of vinylidene chloride and vinyl chloride monomers in aqueous dispersion and in presence of dispersing agent, copolymerization initiator, and subsequently added polymerization stopper, after which unreacted monomers are removed and copolymer particles are recovered from aqueous suspension and dried. Method is characterized by that copolymerization of vinylidene chloride and vinyl chloride monomers proceeds in presence of plasticizing and thermally stabilizing composition including epoxydized derivatives of carboxylic acid triglycerides and carboxylic acid esters in amounts below or equal to 12% based on the total mass of monomers being copolymerized at weight ratio of above composition to carboxylic acid esters 1:(0.75-6). In this case, the composition can be introduced either in one time in the beginning of the copolymerization process or stepwise: time in the beginning of the copolymerization process but after removal of when unreacted monomers using known procedures. Accordingly, implementation of the invention allows preparation of copolymer particles with improved thermoplastic properties appropriate for manufacturing technical-destination articles through known processes without additional treatment of polymer particles and at temperature by 5-10°C lower. Moreover, the whole technological cycle is simplified owing to exclusion of stages wherein plasticizer should be added to dried copolymer and compound formed therefrom before formation of film. Film materials manufactured from above-described copolymer particles are clear, defectless, and produce no smell.
EFFECT: enhanced copolymerization efficiency.
6 cl, 1 tbl, 5 ex
SUBSTANCE: invention discloses a polymerisation method involving the following steps: (a) reacting aqueous suspension containing an initiator, vinyl chloride and optionally one or more copolymers in a continuous action mixing reactor; and (b) further reaction of the obtained suspension in at least one second reactor; where the degree of conversion of vinyl chloride in the continuous action mixing reactor at step (a) ranges from 10 to 40 wt %.
EFFECT: invention can be used to produce copolymers with excellent heat resistance and constant particle size distribution of the obtained polyvinyl chloride(D50=150 mcm).
14 cl, 2 tbl, 3 ex
SUBSTANCE: copolymers contain the following, in terms of total weight of the copolymer: a) 40-97 wt %, preferably 45-90 wt % perfluoroalkyl ethyl methacrylate, b) 1-50 wt %, preferably 5-30 wt % C12-C22 alkyl(meth)acrylate and c) 0.5-10 wt %, preferably 1-5 wt % of one or more thermally cross-linked or isocyanate-reaction monomers, and d) 1.5-50 wt %, preferably 4-30 wt % vinyl chloride and/or vinylidene chloride. The mixture of perfluoroalkyl ethyl methacrylates has the formula RfCH2CH2OCOC(CH3)=CH2, where RF is a perfluoroalkyl chain and contains 1-70 wt % 4 or less fluorinated carbon atoms and 30-99 wt % 6 fluorinated carbon atoms.
EFFECT: obtaining copolymers and aqueous mixtures of copolymers for finishing fibrous substrates.
7 cl, 7 ex, 3 tbl
SUBSTANCE: method is carried out by aqueous suspension, microsuspension, emulsion or microemulsion polymerisation of at least one halogen-substituted monomer, e.g. vinyl chloride, as an independent component or combined with one or more other vinyl monomers, preferably with content of less than 50 wt % of the one or more other vinyl monomers. The method is characterised by that it includes adding at least one agent which slows down radical polymerisation, which is dialkyl-N,N-substituted hydroxylamine, and at least one perhalogenate as a bleaching agent, wherein the perhalogenate-anion counterion is selected from lithium (Li), sodium (Na), potassium (K), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), zinc (Zn), aluminium (Al), lanthanum (La) and cerium (Ce). Also disclosed is the use of the agent which slows down radical polymerisation with at least one perhalogenate, as indicated above, in the method of producing halogen-substituted polymers, as well as a composition for use in the method of producing halogenated polymers.
EFFECT: obtaining polymers with good whiteness properties and stability of whiteness.
13 cl, 1 tbl, 11 ex
SUBSTANCE: method is described for preparing aqueous solutions of copolymers, involving a fundamental step for copolymerisation of partially neutralised acrylic and maleic acid in the presence of hydrogen peroxide in amount of 2 to 4% of total mass of monomers at temperature ranging from 85 to 105°C in an aqueous medium, which is realised through gradual addition of an aqueous solution of hydrogen peroxide for 3 to 6 hours into an aqueous solution of partially neutralised maleic acid and simultaneous gradual addition of an aqueous solution of partially neutralised acrylic acid, or an aqueous solution of free acrylic acid, or aqueous solutions of free acrylic acid and a base, and subsequent addition of hydrogen peroxide for 30 to 60 minutes after completion of simultaneous addition of hydrogen peroxide and acrylic acid, and a step for pre-polymerisation by keeping the reaction mixture at polymerisation temperature, distinguished by that, the pre-polymerisation step is realised by keeping the reaction mixture at polymerisation temperature for 35 to 60 minutes, subsequent simultaneous addition of aluminium or potassium persulphate in amount ranging from 0.10 to 0.15% of total mass of monomers and subsequent keeping at polymerisation temperature for 45 to 90 minutes.
EFFECT: increased dispersion capacity of copolymers.
1 cl, 1 tbl, 8 ex
SUBSTANCE: flocculant has the following composition, wt %: partial magnesium salt of a copolymer of acrylic and methacrylic acid neutralised by 60% (with ratio of monomers: acrylic acid - 45%, and methacrylic acid - 55%) 2.4-3.5; sodium salt of a copolymer of acrylic and methacrylic acid (with ratio of monomers: acrylic acid - 35%, and methacrylic acid 65%) 3.8-5.8; polyacrylamide 1.1-1.5; water - the balance. The flocculant is used in form of process solutions with concentration 0.015-0.035 wt %. 0.035% aqueous flocculant solutions have the highest flocculating power.
EFFECT: flocculant has high solubility in water and ensures high efficiency when used to clarify waste water.
SUBSTANCE: invention relates to emulsifying polymers and use of these polymers for stable emulsification of hydrophobic additives in aqueous concrete plasticisers. Disclosed is a polymer P, obtained via copolymerisation (a) of at least one ethylenically unsaturated monomer A selected from a group consisting of unsaturated mono- and dicarboxylic acids, sulphonic acids, phosphonic acids in form of free acids or salts or partial salts or halide or anhydride, with (b) at least one ethylenically unsaturated monomer B of formula ,
where radicals and coefficients are as described in the claim and (c) with at least one ethylenically unsaturated monomer C of formula
where radicals and coefficients are as described in the claim and with (d) at least one ethylenically unsaturated monomer D of formula
where radicals and coefficients are as described in the claim and optionally (e) with at least one basic ethylenically unsaturated monomer E of formula ,
where radicals and coefficients are as described in the claim and optionally (f) with at least one other ethylenically unsaturated monomer W. Use of the polymer as a plasticiser for water-curable compositions and a water-curable composition are also disclosed.
EFFECT: polymer improves quality of mortar.
19 cl, 5 tbl
SUBSTANCE: group of inventions relates to curable water-based composition for obtaining coating on non-woven material, method of manufacturing treated non-woven material, treated with curable water-based composition, and non-woven material, treated with composition. Composition includes copolymer and cross-linking agent. As copolymerised units aid copolymer contains from 1 to 10 wt %, counted per dry weight, of itaconic acid copolymer and from 90 to 99 wt % of copolymerised ethylene-unsaturated monomer, selected from the group, including ethylacrylate, butylacrylate, styrene, methylmethacrylate, acrylic acid, methacrylic acid, acrylonitrile and their mixtures. Cross-linking agent has at least two hydrazine groups, with molar ratio of hydrazine group in cross-linking agent to carboxyl group in copolymer constituting from 0.05 to 2. Water-based composition is cured at temperature from 100°C to 250°C.
EFFECT: high tensile strength in dry, wet and submerged into isopropyl alcohol state.
6 cl, 13 tbl, 19 ex
SUBSTANCE: invention relates to methods of producing raw maleic anhydride. In particular, method includes steps where: reactor output stream, containing maleic anhydride, is fed into bottom part of absorption column, where it comes into contact with a non-cyclic solvent, that is fed close to its upper part and is a diester, having a boiling point under normal conditions between 250 °C and 350 °C, solubility of fumaric acid at least 0.06 wt% at temperature of 60 °C, solubility of maleic anhydride at least 10 wt% at temperature of 60 °C, water solubility not higher than 100 mg/l, density, different from water density at least to 0.020 g/ml, and a water-soluble hydrolysis product with molecular weight not higher than that of pentanol, with transfer of maleic anhydride of outlet stream of reactor into a solvent, wherein gas stream to be extracted is blown off from absorption column, and enriched solvent, containing maleic anhydride, is removed from absorption column near bottom of absorber and directed into flash tower near its middle part, untreated maleic anhydride is removed from stripping column near its middle or upper part.
EFFECT: methods make it possible to use cheaper solvent than phthalates.
11 cl, 1 dwg, 1 tbl