DE2330561A1 - PVC paste - prepd in presence of an alkali metal alkenylsulphonate as emulsifie-sifter - Google Patents

Abstract

PVC pastes are mfrd. using >=1 alkenylsuplphonate R-CH=CH-SO3M where M is an alkali metal- or ammoniumion and R is a linear aliph. 6-18C hydrocarbon, as emulsifier during the polymn. and/or working-up of the resulting polymer. The resulting organosols or plastisols readily release enclosed air thus eliminating the need for appln. of extremely low pressures and long venting time.

Description

Pastes based on vinyl chloride polymers, process too their manufacture and use 1, priority: June 70, 1972, Japan, No. 66 056/72 The invention relates to new pastes based on vinyl chloride polymers, a process for their production and their use for the production of coatings and moldings.

It is known that finely powdered vinyl chloride paste resins with a Particle size of about 0.1 to 2μ together with plasticizers, relatively stable dispersions result, which can be gelled to form protective coatings or moldings by heating. In the production of vinyl chloride resin sols by mixing the vinyl chloride paste resin with plasticizers, stabilizers and other additives there is occasionally one Foam development that affects the surface quality and texture of the end project and thus its commercial value also affects the mechanical properties are worsened, the mixture is usually vented during or after Kneading process under reduced pressure These ventilation measures are, however, G borne out and require a relatively long time so that they are cost-effective the known manufacturing process.

Vinyl chloride paste resins are usually made by emulsion polymerization using a water-soluble catalyst or by polymerizing Vinyl chloride in a homogenized reaction mixture using an oil-soluble Catalyst produced. In the polymerization reaction, anionic surfactants become surface-active Agents, e.g. the alkali metal salts or ammonium salts of higher sulfonic acid esters or Alkylbenzenesulfonates, added as emulsifiers.

The vinyl chloride polymer latex produced by emulsion polymerization is then spray-dried, but to increase the mechanical stability of the Latex while drying resp.

to lower the viscosity of the vinyl chloride polymer latex prepared sols in some cases the addition of a suitable amount of the above said anionic surfactants or a nonionic surfactant By means of, e.g. a polyoxyethylene alkyl ether, polyoxyethylene-polyoxypropylene block copolymer, Sorbitan ester or glyceral alkyl ester, required.

In conventional manufacturing processes, however, is also when using the described emulsifiers during the polymerization dic ability of the obtained Sols to release the trapped air only unsatisfactory, so that the paste resin only poor quality.

The object of the invention is therefore to provide an improved method for Production of organosols or plastisols based on vinyl chloride polymers to create the trapped under normal conditions or under reduced pressure Easily release air and thus neither the use of extremely low pressures nor require long venting times.

The invention thus provides a method for producing Pastes based on virnyl chloride polymers, which are characterized is that the polymerization of the vinyl chloride and / or the processing of the obtained vinyl chloride polymer for paste in the presence of at least one alkenyl sulfonate of the general formula I R - CH = CH - SO3M (I) in which N is an alkali metal or Ammonium ion means and F, a straight-chain aliphatic hydrocarbon radical with 6 to 18 0 atoms is carried out.

In a preferred embodiment of the method according to the invention is monomeric vinyl chloride in the presence of said alkenyl sulfonate to one Polyvinyl chloride paste resin polymerized, which then into a sol with extraordinarily improved ventilation can be processed.

The expressions vinyl chloride paste and "sol" are abbreviations for plastisols or organosols made from a vinyl chloride paste resin or its in emulsion polymerization resulting latex and a plasticizer.

In the method of the invention, the vinyl chloride paste resin is through Polymerization obtained in the presence of a special emulsifier and / or the vinyl chloride paste is made in the presence of the special emulsifier.

Compared to using the emulsifier alone in production of the vinyl chloride paste, its use in the polymerization gives a product with improved properties.

However, the best results can be achieved when the special Emulsifier both during the polymerization and during the preparation of the paste is used. Vinyl chloride pastes usually contain plasticizers in one Amount of about 30 to 150 parts by weight, preferably 50 to 100 parts by weight per 100 parts by weight of the vinyl chloride paste resin.

The Meichmaciler used in the context of the invention are subject to no critical conditions and can be arbitrarily among those for vinyl chloride pastes plasticizers used are selected.

The invention relates primarily to polymerization in the presence of a special emulsifier, and only secondarily - there the effects no longer stand out - on the production of vinyl chloride paste from the obtained Vinyl chloride paste resin.

The vinyl chloride paste made by the process of the invention has the distinctive ability to trapped air under normal conditions or easy to dispense under reduced pressure. Under normal conditions this will be Open standing # of the vinyl chlorine paste understood under normal pressure, whereby the # included Air escapes. Under reduced pressure, the paste is left standing at a Understood pressures less than 760 torr.

Plastisols consist of a vinyl chloride paste resin or its latex produced during the polymerization, a plasticizer and, if necessary, stabilizers, Pigments, fillers and other additives while making an organosol from one Plastisol and a diluent composed. Both plastisols and Organosols fall within the scope of the invention.

Preferred compounds among the large number of suitable plasticizers are the phthalic acid esters, e.g. dimethyl, diethyl, dibutyl, dihexyl and dioctyl phthalate, Esters of aliphatic dicarboxylic acids, e.g. di-isoic acid succinate, di-isodecyl adipate and dioctyl sebacate, phosphates such as tricresyl phosphate, fatty acid esters, such as butyl oleate and methyl acetyl ricinoleate, esters of polyhydric alcohols such as diethylene glycol dibenzoate and pentaerythritol methyl ester, epoxy compounds such as epoxidized soybean oil and polyester.

The plasticizers are used in an amount of 30 to 150 parts by weight, preferably 45 to 90 parts by weight per 100 parts by weight of the vinyl chloride paste resin used.

The vinyl chloride pastes of the invention may contain customary ones Stabilizers; special examples are the metal soaps, such as calcium, barium, Zinc and lead stearate, organic tin stabilizers such as dibutyltin dimaleate and dibutyltin- J dilaurate, and chelates such as ethylene diamine tetraacetate. The stabilizers prevent discoloration of the vinyl chloride polymer as a result thermal decomposition or radiation degradation if the plastisol or organosol des Vinyl chloride resin is gelled by heating.

Usually, the stabilizer is used in an amount of about 0.1 to 10 parts by weight per 100 parts by weight of the vinyl chloride paste resin.

Pigments can optionally be added, but the use is prohibited Avoid toxic metal components when the end product is along with food or to be used as a toy. Metal oxides or organic pigments are used as pigments Pigments in question, the amount of which is usually 1 to 10 parts by weight per 100 Parts by weight of the vinyl chloride paste resin.

Diluents are optionally used to adjust the viscosity of the plastisol or organosol. The diluting agent is usually a petroleum hydrocarbon with a boiling point of about 50 to 2500C. To give flame-retardant properties you can use trichlorethylene or tetrachlorethylene.

Filling materials, such as calcium carbonate or clay, are usually used in a Amount of 0 to 200 parts by weight per 100 parts by weight of the vinyl chloride paste resin used.

The components mentioned are made with the help of a niche device, e.g. a grinding plant, a kneader, a Hobart mixer, a roller mill or a ball mill, evenly mixed into an organosol or plastisol. The diluent is only added in a suitable amount to achieve the desired organol sol viscosity to adjust.

The particular emulsifiers of the invention are used either alone or in combination with known emulsifiers in the polymerization of monomeric vinyl chloride optionally added with other copolymerizable monomers, e.g. monoolefins, where an extremely stable polymerisation system arises at /.

On the other hand, the emulsifiers of the invention can be used following the Polymerization can be added, whereby e.g. the resulting during the polymerization Latex good mechanical stability, the vinyl chloride organosol or plastisol obtained good ventilation properties and the end product, e.g. the gelled protective coating or molded articles, good electrical properties can be imparted. The special ones Emulsifiers of the invention can therefore be used at any stage of processing from the latex stage can be used up to the vinyl chloride paste stage, e.g. during drying, milling and other processing steps involved in making a Vinyl chloride paste made from a vinyl chloride paste resin are common. In the practical To carry out, the latex formed during the polymerization is mixed with the Emulsifier to give it during the drying process, e.g. spray drying or plate drying, or to give the subsequent grinding the desired properties, and capable of g then with the plasticizer and the other additives.

In this embodiment, in which the special emulsifiers Invention can only be used in the production of vinyl chloride paste the polymerization can also be carried out alone in the presence of a known emulsifier. However, this embodiment is not preferred because the results obtained are less are more favorable than when using the special emulsifiers of the invention for the polymerization or in particular during the polymerization and for the production of the paste.

In all of these embodiments, however, the emulsifiers make possible the invention results in far better results than known emulsifiers. The emulsifiers are also less toxic than common emulsions; furthermore, they will go through Microorganisms are easily broken down, so that the emulsifier waste is not processed can.

The emulsifiers of the invention can be used in emulsion polymerization of vinyl chloride or when processing to vinyl chloride pastes, without that with common anionic emulsifiers, e.g. alkali metal or ammonium salts higher sulfonic acid esters, alkali benzenesulfonates or dialkyl sulfosuccinates Difficulties arise. Particularly good results can be achieved if the emulsifiers are used for the polymerization. In this case. owns that the resulting paste resin produced sol the ability to trapped air easy to dispense, and practically no polymeric deposits form during the polymerization.

Specific examples of the emulsifiers of the invention are sodium a-octenyl sulfonate, Sodium a-decenyl sulfonate, sodium a-dodecenyl sulfonate, sodium a-tetradecenyl sulfonate, Sodium ahexadecenyl sulfonate, sodium a-octadecenyl sulfonate, ammonium aoctenyl sulfonate, Ammonium a-decenyl sulfonate, ammonium dodecenyl sulfonate, ammonium a-tetradecenyl sulfonate, Ammonium a-hexadecenyl sulfonate and ammonium a-octadecenyl sulfonate.

The emulsifiers of the invention are usually used for emulsion polymerization in an amount of 0.05 to 5.0 percent by weight, preferably 0.1 to 2.0 percent by weight, based on the monomers to be polymerized, and when used for paste production in an amount of 0.001 to 1.0 percent by weight, preferably 0.01 to 1.0 percent by weight, based on the polymer content of the latex.

Even when carrying out the polymerization with a mixture of emulsifiers Invention and other common anionic and / or nonionic emulsifiers the deaerability of the sol prepared from the paste resin obtained is satisfactory. however, preferably the emulsifiers of the invention make up at least 50 percent by weight the total emulsifiers used for polymerization or paste production the end.

In the process of the invention, of course, mixtures of the specific Emulsifiers or their mixtures with known emulsifiers with the same success can be used. The above quantitative data then apply accordingly.

The vinyl chloride paste resin of the invention is prepared by conventional emulsion polymerization, e.g., by polymerization using of starting polymer (“seeded polymerisation11), polymerisation with addition of the emulsifier (emulsifier addition method) or homogeneous polymerization under Use of an oil-soluble catalyst.

The process of the invention is thus not limited to a specific emulsion polymerization process limited as the emulsifiers of the invention improved results in all of these cases deliver. The process is everywhere where the emulsifying effect is important the invention can be used with advantage. Specific examples of suitable polymerization processes, in which the emulsifiers of the invention are applicable are set forth in US patents 3,551,399, 3,324,097 and 2,520,959. The first mentioned patent concerns a method of emulsion polymerization using an oil-soluble peroxide in a homogeneous reaction system. The emulsifiers of the invention are used here preferably used alone and optionally in a broader percentage range. An emulsion polymerization process using starting polymer is e.g. in I.N. Kolthoff, E. J. Meenan and C. W. Carr, Journal of Polymer Science, Vol. 7 (1951), p. 577.

The expression "vinyl chloride paste resin" does not only include vinyl chloride homopolymers but also vinyl chloride copolymers. These copolymers for paste production contain at least 50 percent by weight, preferably at least 70 percent weight percentage, Vinyl chloride copolymerized with other monoolefinic monomers. Specific Examples of such monoolefins are vinyl acetate, vinylidene chloride, acrylonitrile, Acrylic acid esters and unsaturated acids such as maleic acid.

During the polymerization, higher aliphatic acids such as Palmitic acid or stearic acid, higher alcohols such as dodecyl alcohol and stearyl alcohol, Metal salts such as sodium sulfate and sodium phosphate, or hydrocarbons such as Alkylbenzene or dodecane, as dispersion stabilizers together with the emulsifier can be used. Finally, you can use the nonionic emulsifiers mentioned use in conjunction with the emulsifiers of the invention.

The examples illustrate the invention.

EXAMPLE 1 A 300 liter, glass-lined The autoclave is filled with 125 kg of demineralized water and 5 kg of a latex from g). egg Formed vinyl chloride starting polymer with a particle size of 0.4 P charged, which contains 2 kg of polyvinyl chloride. After the oxygen has been driven off, the mixture becomes mixed with 100 kg of monomeric vinyl chloride. This is at around 500C and one Polymerized under pressure of 7.5 atmospheres in the presence of potassium persulfate, over the total polymerization time 0.05 percent by weight (3.5 g / hour) vinyl chloride continuously be fed into the autoclave. From the point in time when the degree of polymerization is reached from 18 percent to @ complete polymerization is given in Table I. Emulsifier continuously at a rate of 0.025 weight percent / hour (total 0.35 percent by weight), based on the monomeric vinyl chloride, in the autoclave fed in. After 14 hours, the polymerization is interrupted and that is not converted monomers withdrawn. Polymer agglomerates in the latex or deposits the stirrer blade and the autoclave walls are collected, dried and weighed. The latex obtained is spray-dried under constant conditions and becomes one Powdered vinyl chloride resin. The amount of polymer agglomerates as well as the ability the brine produced from the individual paste resins to release trapped Air under normal conditions and under reduced pressure are given in Table I.

Table 1 Poly emulsifier mean (a) (b) (c) merisate particle size of the polymer (; l) A sodium a-tetrad 0.8 0.1 4 0 cenyl sulfonate B sodium α-dodece- 0.8 0.05 10 nylsulfonate, comparative example C, sodium dodecylben- 0.8 ° 5 30 18 zene sulfonate D Sodium Lauryl Sulphate 0.8 0.4 12 5 Note: (a) Amount of polymer agglomerates as Percentage of monomer weight; (b) ventability under normal conditions; (c) Can be vented under reduced pressure.

The ventilability under normal conditions or under reduced Pressure is determined as follows: 60 g of the vinyl chloride paste resin, 40 g of dioctyl phthalate and 1 g of a Cd-Ba-Zn liquid stabilizer are mixed together, and the plastisol obtained is placed in a 500 ml beaker. In the case of ventability the beaker with the plastisol is placed in a vacuum desiccator under reduced pressure placed and defoamed for 5 minutes at 50 Torr. In both cases the sol Left to stand for 1 hour at room temperature, then poured onto a glass plate and after setting a layer thickness of 0.2 mm with the help of a doctor blade Gelled in an oven for 5 minutes at 1700C.

Then the number of foam bubbles in circles of 0.5 mm Diameter at three arbitrary points of the obtained film using one Microscope determined. The mean value obtained is then a measure of the ventilability, where lower values are to be assessed as a better result.

From the results summarized in Table 1, it can be seen that that made using sodium α-olefin alkyl sulfonates as emulsifiers Vinyl chloride sol excellent ventilation under normal conditions or below has reduced pressure, and that only small amounts of polymer agglomerates are formed.

Example 2 A 300 liter glass lined autoclave is mixed with 200 kg of demineralized water, 100 kg of vinyl chloride, 0.05 percent by weight, based on the monomer a, a'-azobis- butyrovaleric acid nitrile, 0.6 percent by weight, based on the monomer, cetyl alcohol and 0.6 percent by weight, based on the monomer, of the emulsifier given in Table II. the resulting polymer solution is then 3 hours at room temperature with the aid of a Stirred homogenizer. This is followed by polymerization for 13 hours at about 50 ° C. and one hour Pressure of 7.5 atm until complete polymerization. Either way are practical no polymer agglomerates detectable in the resulting latex; also the stirrer blade and the autoclave wall shows no polymer deposits.

According to Example 1, a paste is produced from the latex, which is also is tested according to Example 1 for their ventilability. The results obtained are shown in Table II.

Table II Polymer emulsifier mean part (b) (c) table size of the polymer (u) E sodium a-stearenyl 0.8 0 0 sulfonate F sodium a-tetradecenyl 0.8 0 0 sulfonate comparative example G sodium dodecylbenzene 0.8 31 18 sulfonate H Sodium Lauryl Sulphate 0.8 19 10 Note: (b) and (c) see Table 1.

Example 3 According to Example 2, 90 kg of vinyl chloride and 10 kg of vinyl acetate are used polymerized instead of 100 kg vinyl chloride. In any case, the No polymer deposits found on the stirrer blade and on the autoclave wall. A paste is produced from the resulting latex according to Example 1, which is also according to Example 1 for their ventability under normal conditions or under reduced Pressure is checked. The results obtained are shown in Table III.

Table III Emulsifier Average particle (b) (c) particle size of the polymer (y) I sodium a-stearenyl 0.8 0 0 sulfonate J sodium a-tetradecenyl 0.8 0 0 sulfonate Comparative Example K Sodium Dodecylbenzene 0.8 4.6 19 sulfonate sodium lauryl sulfate 0.8 20 6 Note: (b) and (c) see table I.

From Tables II and III it can be seen that according to the method The products manufactured according to the invention have excellent ventilation under normal conditions and under reduced pressure. When comparing Examples 2 and 3 with the polymerization using a starting polymer from Example 1 shows that the comparative examples 2 and 3 better ventilability under normal conditions and under reduced pressure result as comparative example 1. However, the deaerability is that by polymerization in the presence of an oil-soluble The catalyst and the products produced by the emulsifiers according to the invention are far superior.

Example 4 The polymer latices @ A, C, D, G and H from the examples 1 and 2 are used to produce a vinyl chloride paste with 0.1 percent by weight, based on the polymer weight, mixed sodium adodecenyl sulfonate as an emulsifier. The latices are then dried according to Example 1 and given the vinyl chloride resin A1, C1, D1, G1 and H1 pulverized.

In addition, by adding 0.1 percent by weight, based on the Polymer weight for the preparation of the polymers C, D, G and H in the examples 1 and 2 used polymerization emulsifiers for the polymer latices C, D, G and H made paste resins C2, D2, G2 and 112.

The sols produced using the paste resins obtained are according to Example 1 on their ventilability under normal conditions and under checked under reduced pressure. The results obtained are shown in Table IV.

Table IV Polymer Emulsifier (b) (c A1 sodium dodecenyl sulfonate O 0 C1 1? 1 10 3 Dz "" 4 1 G1 "n 9 q 3" "5 1 Comparative examples C2 Sodium dodexylbenzene numerous foam sulfonate bubbles D2 sodium lauryl sulfate 19 8 G2 sodium dodecylbenzene numerous foam sulfonate bubbles H2 sodium lauryl sulfate 28 13 Note: (b) and (c) see Table I.

The results show that the emulsifiers of the invention also act as Additives in the production of pastes result in brine with excellent deaerability.

Claims (1)

P a t e n t a n s p r ü c h e 1. Pastes based on vinyl chloride polymers, d a d u r note that they are made using at least one alkenyl sulfonate of the general formula I. R - CII = CH - SO3M (I) in which M is an alkali metal or ammonium ion and R is a straight-chain aliphatic hydrocarbon radical with 6 to Represents 18 carbon atoms, as an emulsifier in the polymerization of vinyl chloride and / or produced during the processing of the vinyl chloride polymer obtained into paste have been. 2. Pastes according to claim 1, characterized in that the vinyl chloride paste resin consists essentially of polyvinyl chloride. 3. Pastes according to claim 1, characterized in that the vinyl chloride paste resin essentially composed of a copolymer of vinyl chloride and other monoolefinic ones Monomers with a vinyl chloride content of at least 50 percent by weight. 4. Pastes according to claim 3, characterized in that the copolymer Contains at least 70 percent by weight vinyl chloride. 5. A method for producing the pastes according to claim 1, characterized in that that the polymerization of vinyl chloride and / or the processing of the obtained Vinyl chloride polymer for paste in the presence of at least one alkenyl sulfonate of the general formula I R - CII = CII - S03M (I) in which M is an alkali metal or Ammonium ion is and R is a straight-chain aliphatic hydrocarbon radical represents having 6 to 18 carbon atoms. 6. The method according to claim 5, characterized in that the Polymerization of the vinyl chloride in the presence of 0.05 to 5.0 percent by weight of the Alkenyl sulfonate, based on the monomers to be polymerized, performs. 7. The method according to claim 5, characterized in that one for Production of the vinyl chloride paste 0.001 to 1.0 percent by weight of the alkenyl sulfonate, based on the vinyl chloride polymer obtained in the polymerization, used. 8. The method according to claim 5, characterized in that in addition to the alkenyl sulfonate another, in the polymerization of vinyl chloride and / or Usual emulsifier used in the production of vinyl chloride pastes; however the alkenyl sulfonate at least 50 percent by weight, based on the total amount of emulsifier, matters. Process according to Claim 5, characterized in that the emulsion polymerization is carried out using exit @@@@@. meri sat performs. 10. Verfaii'c-n according to claims 5 and C, characterized in that that the emulsion polymerization is carried out with the addition of an emulsifier. 11. The method according to claim 5, characterized in that @@@ the Emulsion polymerization using an oil-soluble catalyst in one homogeneous system. 12.Verfahren according to claim 5, characterized in that @@@ the Emulsion polymerization of vinyl chloride using vinyl chloride starting polymer in the presence of an oil-soluble catalyst and from 0.1 to 2.0 percent by weight of the alkenyl sulfonate, based on the monomers to be polymerized. 13. Use of the pastes according to claims 1 to 4 for preparation of shaped structures and coatings.