CS210702B1 - Manufacturing process of suspension types of homopolymers and/or copolymers of vinyl chloride - Google Patents

Description

According to the present invention, technically readily available complexing additives are readily prepared by slurry polymerization or copolymerization with other monomers in the presence of controlled amounts. products with very good phyto-chemical and mechanical properties, in particular suspension polyvinyl chloride with high grain porosity, narrow grain distribution, high bulk density and fast flowability ”.

Previous Author Certificate # 162 899 discusses the prior art in more detail, specifying in detail the individual ingredients in the suspension polymerization system. The use of polyvinyl alcohol alone, respectively. Although the partially saponified polyvinyl acetate as dispersant is known, high molecular weight and / or high molecular weight are generally required. a high polymerization degree of 1,500 to 1,700 and an acetate content of up to 25% by Lberman E. N. Polučenije i svivivililchlorida, str. 68, Izdatelstvo: Khimija, Moskva / 1968 / J.

Such a partially divided polyvinyl acetate requires a technically demanding preparation, is prepared at a relatively low polymerization rate and is not optimal in terms of its influence on the properties of the suspension PVC. It is also known to use hydroxypropyl methylcellulose, hydroxypropylcellulose and hydroxyethylcellulose as dispersants and / or dispersants. protective colloids in suspension after polymerization and copolymerization of vinyl chloride.

However, their amounts and the choice of a suitable continence are important, and if these are not preserved, a good suspension will not be obtained. Only their optimal amounts provide high bulk density, suitable porosity, narrow distribution and good morphology, and other optimal properties in terms of technical and general utility properties of suspension homopolymer PVC ^; or even a plurality of polymers. A disadvantage of the known processes is the fact that they protect only the individual ingredients, and they are not mentioned further in the examples and in the description, which do not ensure the creation of conditions for grain formation of optimal properties.

According to the present invention, a process for the production of suspension types of homopolymers and / or copolymers of vinyl chloride according to U.S. Pat. 162 899 with a dispersant system based on aliphatically substituted hydroxycelluloses and at least one other surfactant such that, as part of the dispersant system, in addition to alkylhydroxypropylcellulose, preferably methylhydroxypropylcellulose with a methoxy group content of 26 to 29% and propylene glycol ether Preferably, the partially diluted polyvinyl acetate and the polyvinyl acetate are applied. industrial polyvinyl alcohol with an average molecular weight of 15,000 to 45,000, preferably 18,000 to 25,000, with an acetate content of 10 to 18% by weight, preferably 13 to 16% by weight, in an amount of 0.005 to 0.04% by weight, preferably 0.01 to 0.02% by weight, calculated on the monomers, and partially esterified aliphatic polyols with saturated and / or unsaturated acids C-C _9A , preferably C-C.

2 4 12 ^{3Ζ C} 18 ^{a 'but} b ° ⁸ partially zraydelnenými tukraí, wherein as a further surfactant is applied to at least one of the ingredients: hydroxypropyl methylcellulose containing 19 to 24 from methoxy and 4-12 from propylene glycol ether groups, hydroxyalky1celulóza and / hydroxyalkenylcelulóza % of carbon and alkyl or in alkenyl 2 to 5, in a total amount of 0.001 to 0.2% by weight, preferably 0.005 to 0.03% by weight, calculated on the monomers.

The method according to the present invention follows or is dependent on MS. 162 899. However, it should be explained in more detail that other surfactants are: hydroxypropylmethylcellulose, which differs from the first type used as part of the dispersing system, in particular the lower content of methoxy groups, further hydroxyethylcellulose, hydroxybutylcellulose, hydroxyisobutylcellulose, hydroxypentylcellulose and hydroxypentenylcellulose, as well as mixed hydroxyalkylethercelluloses, prepared by the action of a mixture of oxiranes on cellulose, e.g. by treating a mixture of butene oxide, isobutene oxide and butadiene monoxide.

The advantage of the method according to the invention is firstly to find a critical connection between the amounts of individual additives in the polymerization system and its optimum application from the viewpoint of the process and in particular the properties of suspension PVC and copolymers, application of a new technically readily available type of partially saponified polyvinyl acetate of defined properties; the availability of several types of partially esterified polyols, respectively. partially saponified fats, based on technically widely available raw materials.

Other advantages and advantages of the method of the invention are evident from the examples.

Example 1

In a 5 L stainless steel autoclave equipped with an anchor stirrer / 180 fig. 2 200 g of distilled water are weighed / min and 0.7 g of hydropropylmethylcellulose / methylcellulose propylene glycol ether / known under the trade name Methocel 50 F, 0.61 g of hydroxypropylcellulose under the trade name Klucel J, 0.4 g of partially saponified polyvinyl acetate are weighed, respectively. industrial polyvinyl alcohol in the form of an aqueous solution known under the trade name Slovol R (manufacturer) Chemické závody W. Pieck, n. p., Novaks / approximate composition: 16-1.5 wt. dry matter, content of acetate groups 14,5 - 0,8% by weight, Art. acidity 4 mg KOH / gj no. saponification 130 - 15 mg KOH / g (viscosity 4 F aqueous solution 11 to 15 mPa.s), average molecular weight 18,000 to 25,000.

Next, 0.6 g a mixture of unsaturated alcohols and saturated C ₁ to C _2Q / CH ^{and C} i6 = 5% wt .;

r = 5 to 15% by weight; _C10-75 to 85% by weight; up to C of 5 wt. water content up to 0.5% by weight,

18 20..

no. saponification max. 4 mg KOH / g; hydroxyl numbers 195 to 210; the iodine number according to Hanusa 80 /, known under the trade name H, adenol 80, in addition 2 g trichlorethylene, 0.1 g NaOH, 0.2 g

2,6-di-tert-butyl-4-methylphenols, 3.5 g of bis- (4-tert-butylcyclohexyl) percarbonate known by the trade name Perkadox 1662 F with a peroxide content of 98 wt. and 3.5 g diuroyl peroxide. Finally, 1.5 g of partially esterified polyols are added as secondary dispersants and, after air removal, 1,730 g of vinyl chloride.

After 1-meage, it was conducted until a positive pressure drop of 0.3 MPa occurred. The results obtained, depending on the type of secondary dispersant, are given in Table 1. The conversion of the liquid to reach 89 3 The product is dried at 55 ° C.

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CL CL i-CL Π} · Η CL Ό without dispersant reference 8 67 400

Example 2

Weigh 23 kg of distilled water, 9.1 g of hydroxypropylmethylcellulose (28 Z) and propylene glycol ether 6 Z (known under the trade name Methocel 65 HG) into a 50 L stainless steel autoclave (160 ipm). 2.7 g of another type of hydroxypropyl methylcellulose (containing methyl groups 7 7 _and propylene glycol ether 9 Z), known under the trade name Methocel 90 HG and 18.2 g of steam. saponified fats, respectively. of a mixed glycerol ester with stearic acid and unsaturated acids, mainly with oleic acid / mol. weight = 467; From mass. OH = 5.41; no. an acidity of 4.2; no. saponification = 154.5 mg KOH / g; bromine number = 24.6 g-Br / 100 g; bt max. 40 [deg.] C .; glyceride content max. 30 From mass, no. acidity = 10 mg KOH / g; water content max. In addition, 15 g of a mixture of mainly unsaturated alcohols up to C20 / water content max. 0.5% by weight, no. saponification max. 4 mg KOH / g; hydroxyl number 205 and iodine number 80), 20 g of trichloro-thylene, 45.5 g of di-auroylperoxide, 7.2 g of bis- (4-tert-butylcyclohexyl) percarbonate and after removal of air 18.2 kg of vinyl chloride.

Water module. Thus, the polymerization temperature is 56-0.2 ° C, to decrease

- 2 _Λ .

overpressure of 0.3 MPa / 3 kp.cm / occurs in 8 h. The obtained polyvinyl chloride suspension is dried at 50 ° C. Susp. its K value is 65.8; plasticizer absorption 13 min; bulk density 540 g / l; fisheye ”0/10 min; sieve analysis: sieve residue with 0.250 mm aperture is 0.5 Z and overflow through a sieve with apertures below 0.063 mm 8.5 Z

Example 3

In a 15 m stainless steel autoclave equipped with an impeller stirrer (130 Fig. 7 min), two technologies (A, B and A ^, B ^) were compared, with protective colloids, ammonia, secondary dispersants and then trichloroethylene added to the aqueous phase. modifiers and initiators, and finally, after closing the autoclave and removing the air, vinyl chloride.

The actual polymerization is carried out at a temperature of 55 and 55 ° C, respectively. 56 ° C until the overpressure - 2 dropped by 0.3 MPa / 3 kp.cm /. The main differences are in the composition of the batch, but in particular in the quality of the obtained suspension polyvinyl chloride, as shown in Table 2.

Hydroxypropylmethylcellulose (Methocel 50 F), hydroxypropylcellulose (Klucel J), a mixture of unsaturated alcohols up to C18 (Hadenol 80) and partially saponified to polyvinyl acetate and the like.

industrial polyvinyl alcohol (Sloviol R) is already specified in the previous examples.

Table 2

pointer A Technology ^A 1 /experiments/ B ^B 1 temperature, / ° C / ⁵⁵ 56 57 58 demineralized. water / kg / 8 500 7 000 8 500 7 000 vinyl chloride (VC), / kg / 4 500 5 430 4 500 5 523. surfactants: -hydroxypropylmethylcellulose / Methocel 50 F type, / kg / 4.25 1.52 4.25 1.45 -hydroxypropylcellulose / type Klucel J /, / kg / 0.00 1, 20 0.00 0.8 -technical polyvinyl alcohol / Sloviol R / kg / 0.00 0.55 0.00 0.8

pointer Technology / Experiments / A ^A 1. B B, - mixed glycerol ester s kys. stear and oil . / Emulsifier C /, / kg / 0.00 3.50 0.00 3.0 trichlorethylene, / kg / 7.5 3.50 40.0 35.0 oleyl alcohol, respectively, mixture unsaturated alcohols up to C ^ q / Hadenol 80 /, / kg / 4.0 2.0 0.00 0.00 nh ₃ , / kg 0.02 0.02 0.02 0.02 2,6-di-tert-butyl-4-methylphenol (Antioxydant K 2), (kg) 0.00 0, 10 0.00 0.00 dilauroyl peroxide, / kg / 3.00 4.00 3.00 4.00 bis - / - 4-butylcyclohexyl / percarbonate, / kg / 1, 30 1, 60 1.16 1, 30 pressure drop, / MPa / 0.3 0.3 0.4 0.4 polymerization time, / h / 1 2 8 . 11.5 7.5 vývýk susp..polyviny1- chloride, (Z) 86 86 85 89 analýza susp. polyvinylchloride - K value 65.4 68 - 1,5 62.5 62.0 - bulk density, / g / 1 / 420 570 460 600 - absorption of plasticizer, / Min / 1 2 11 - - - network alysis, the rest on sieve 0,25 mm /% / 0.3 0.5 0.5 0.5 overflow through sieve 0,063 mm, /% / 2 1,8 5 3 1,8 8 thermal stability / overall b ieloba in W! 63 70 56 65 In terms of polymerisation consistency quality product with similar results also achieved using diisopropyl peroxydicarbonate instead of bis - / - 4-tert-butyl cyclohexyl / - percarbonate, as well as when the initiators mentioned you were looking from the default raw materials' in sieve "according to MS. 155 869, 163 502, 169 966 and 170,326. Example 4 The procedure is similar to that of the example 3, technology / experiment / B only place 0.8 kg hydro

0.7 kg of hydroxyethyl cellulose and 0.1 kg of butenyl hydroxy cellulose are used. The bulk density of the slurry PVC obtained was 590 g / l, the sieve residue was determined to be 0.25 mm 0.6% and the sieve overflow was 0.063 mm 12 Z.

Claims (1)

OBJECT OF THE INVENTION The process for the production of suspension types of homopolymers and / or copolymers of wine 1 chloride according to U.S. Pat. 162 899 with a dispersant system based on aliphatic substituted hydroxycelluloses and at least one other surfactant, characterized in that, as part of the dispersant system, in addition to alkylhydroxypropylcellulose, preferably methylhydroxypropylcellulose with a methoxy group content of 26 to 29% and propylene glycol ethers Preferably, the partially saponified polyvinyl acetate, respectively, is applied. industrial polyvinyl alcohol having an average molecular weight of 15,000 to 45,000, preferably 18,000 to 25,000, with an acetate content of 10 to 18% by weight, preferably 13 to 16% by weight, in an amount of 0.005 to 0.04% by weight, preferably 'from 0.01 to 0.02 wt., calculated on the monomers, and partial esters of aliphatic polyols £ ikované of saturated and / or SY-NENA in aerosols acid t-C ^, ^Vol positively advantageous ^C n to ^C 18 and / or a partially saponified fats, wherein at least one of the following surfactants is applied: hydroxypropylmethylcellulose containing from 19 to 24 of the methoxy groups having from 4 to 12 of the propylene glycol ether groups, hydroxyalkylcellulose and / or hydroxyalkenylcellulose having a carbon number of from 2 to 5 alkyl or alkenyl; a total amount of 0.001 to 0.2 wt.%, preferably 0.005 to 0.03 wt.%, based on the monomers.