EA013124B1 - Method of producing plasticizer for polyvinyl chloride resins - Google Patents

Abstract

The invention relates to halogen containing compounds, in particular, to a process of producing chlorohydrocarbon plasticizer for polyvinyl chloride linoleum. For replacing toxic phthalic plasticizer and for improving physical-mechanical properties of polyvinyl chloride linoleum a mixture of return paraffin stillage bottoms of sulfonol production is used as hydrocarbon feed material comprising C-Cn-paraffins and C-Calkylbenzene with the following component ratio, wt%: C-C-n-parafins 76.0-80.0; C-Calkylbenzene 76.0-80.0; NNethyldiamine of dimethylphosphonic acid is used as complex on in the amount of 0.01-0.02 of the initial wt% feed material, the chlorination process is carried out at mass ratio hydrocarbon and chlorine mixture equal 1:1-1.8 at 100-105°C. The optimum content of “Chloroplast” in the polyvinyl chloride composition is 25-27 wt% and all physical/mechanical properties of the fabricated linoleum correspond to GOST 1462-79-a.The proposed “Chloroplast” plasticizer is 20 times less toxic and several times cheaper than the phthalic plasticizer.

Description

The invention relates to organic chemistry, specifically to a method for producing a chlorinated plasticizer of polyvinyl chloride linoleum.

A known method of producing a plasticizer for polyvinyl chloride resins. The Plast plasticizer is obtained by treating vat residues of cobalt regeneration with a 3% solution of calcium hypochloride at 25 ° C for epoxidation of double bonds and neutralization of organic acids and distillation of light hydrocarbons at a residual pressure of 5 mm Hg. and cube temperature 210 ° С. The results of testing adhesive tape based on PVC using plasticizer "Plast". It is shown that industrial samples of adhesive tape meet the requirements of technical conditions. Therefore, the Plast plasticizer can be used to replace the expensive plasticizer of the DOF brand by 33%, which will allow to obtain a significant environmental and economic effect (1).

The disadvantage of this method is the multi-stage process.

A known method of producing chlorohydrocarbons plasticizer polyvinylchloride linoleum. As the feedstock used, wt.%: 58-60 C ₁₀ -C ₁₇ n-paraffins, 17-22 C ₁₀ -C ₁₄ alkylbenzenes and the rest C ₂₂ -C ₂₉ solid paraffins. The chlorination process is carried out at a temperature of 100-120 ° C in the presence of a mixture of acetic acid and aniline 0.015-0.03 wt.% From the feedstock. The process is carried out with a mass ratio of chlorine and a mixture of hydrocarbons equal to 0.67-2.4-1.0, the reaction products are blown with an inert gas and stabilized with an ED-20 epoxy resin in an amount of up to 2 wt.% Of the obtained product.

The content of bound chlorine in the composition of the finished product is 22.0-55.0 wt.%. The thermal stability of the chlorinated mixture at 140 ° C is 36-40 min (2).

The disadvantage of this method is the use of solid paraffins in the composition of the feedstock, which helps to reduce the frost resistance of linoleum.

A known method of producing chlorinated paraffin used for plasticization of polyvinyl chloride. The feedstock used is the sulfanol production waste — the bottom residue of the distillation of n-paraffin containing 20-57 wt.% Alkylbenzenes and the rest is the fraction of n-paraffins C ₁₀ C ₁₆ , and the process is carried out at a weight ratio of the bottom residue and chlorine of 1: (1- 3.3) at a temperature of 110-120 ° C.

The resulting chlorinated mixture of C ₁₀ -C ₁₆ n-paraffins and C ₁₀ -C ₁₄ alkylbenzenes with a content of bound chlorine of 25.7-49.0 wt.% Is called Chloroplast-340. To improve the thermal stability of chloroplast-340 after treatment with nitrogen, an epoxy resin of the ED-20 grade is added to 2 wt.%.

PVC compositions are proposed, in g: PVC - 356; DOF - 39.0; chloroplast-340 - 156; asbestos - 377; T1O ₂ 36; calcium stearite - 4; pigment - 1, up to 80% chloroplast-340 by weight of plasticizer was used. All indicators of the obtained linoleum meet the requirements of normative and technical documentation with the exception of frost resistance (3) (prototype).

The disadvantages of the method are, in the presence of Fe ions in the composition of the starting products, the implementation of chlorination without complexions and, accordingly, the dark color of chloroplast-340, low frost resistance of linoleum.

The objective of the invention is to obtain transparent chlorinated plasticizers based on the VAT residue of sulfonol and the replacement of dioctyl phthalate in the composition of the PVC composition with chloroplasts.

The problem is solved by chlorination of the bottom residue of distillation of reverse paraffin containing C10C ₁₆ n-paraffins and C ₁₀ -C ₁₆ alkylbenzenes, in the following ratio, wt.%: C ₁₀ -C ₁₆ n paraffins 76-80 and C ₁₀ -C ₁₆ alkylbenzenes 20- 24, ethylene diamine-ΝιΝ ¹ dimethylphosphonic acid, taken in an amount of 0.015-0.02 wt.% By weight of the feedstock, is used as complexon, and the chlorination process is carried out at a mass ratio of a mixture of hydrocarbons and chlorine equal to 1: 1-1.8 at temperature of 100-105 ° C.

Upon reaching the specific gravity of chlorohydrocarbons 1120-1300 g / cm ^{3 the} process is considered complete. Then the reaction mass is cooled to 80-90 ° C, chlorine is closed, and for blowing off the residual chlorine and hydrogen chloride, a nitrogen supply is turned on for 30 minutes at a speed of 60 l / h.

226 g of chlorohydrocarbons are obtained. Yield 98.7% of theory on raw materials taken. The content of bound chlorine after stabilization of the final product of 2 wt.% Epoxy resin ED-20 is 25.0-46.0 wt.%.

Chlorinated mixtures of C ₁₀ -C ₁₆ n-paraffins and C ₁₀ -C ₁₆ alkylbenzenes are hereinafter referred to as chloroplast-300; the number 300 indicates the molecular weight of the product. Chloroplast-300 has a flash point of 211-238 ° C, thermal stability at 140 ° C for 30-40 minutes, acidity according to HC1 0.002-0.003%, viscosity according to VZ-4 at 20 ° C 1000-1500 s. The yield on the taken raw materials is 90.6-99.1 wt.%. The results of the experiments are presented in table. one.

A polyvinyl chloride composition using chloroplast-300 is proposed, obtained according to Example 2 on laboratory rollers at 140 ° C, the rolling time is 8-10 minutes. After processing the polyvinyl chloride composition, the resulting linoleum is subjected to a laboratory test for absolute and permanent deformation, abrasion and linear dimensions. Physico-mechanical indicators of linoleum (deformation during indentation, abrasion, shrinkage) are determined according to GOST 1463279, they are presented in table. 2.

- 1 013124

Physico-chemical properties of the bottom residue of distillation of reverse paraffin sulfanol production

The composition of the bottom residue, weight. %: С; о-С; йН- paraffins 76 ^ -80 CngSm alkyl bin ash 204-24 Beginning of boiling point, ⁰ С 200 Specific gravity, not less than g / cm ³ 0.744-0.800 Humidity, not more than weight. % 0.5 Auto-ignition temperature, ¹¹ C 2004-310 Contents Ge ₂ Oz, weight. % 0.015

For a better understanding of the invention, the following are examples.

Example 1. In a tubular pyrex reactor (diameter 45 mm, height 500 mm) with a sealed pyrex filter load 150 g of a mixture of 76% C ₁₀ -C ₁₆ n-paraffins and 24% C ₁₀ -C ₁₆ alkylbenzenes.

The mixture is heated to 100 ° C with stirring with nitrogen and 0.015 g of complexone, ethylenediamine-L1-dimethylphosphonic acid, is added. Then the nitrogen is closed and within 120 minutes 150 g of evaporated chlorine are fed into the lower part of the reactor. Chlorination is carried out at a mass ratio of the initial hydrocarbon feed to chlorine of 1: 1: 1.8 and a temperature of 105 ° C. Upon reaching the specific gravity of chlorocarbons 1120-1300 g / cm ^{3 the} process is considered complete. Then the reaction mass is cooled to 80-90 ° C, the chlorine is closed, and for blowing off the residual chlorine and hydrogen chloride, the nitrogen supply is turned on for 30 minutes at a speed of 60 l / h.

226 g of chlorohydrocarbons are obtained, yield 98.7% of theory on the taken raw materials. The content of bound chlorine after stabilization of the final product of 2 wt.% Epoxy resin (ED-20) is 33.0%.

The conditions and results of the experiments are given in table. one.

Example 2. The process is carried out as in example 1, with the exception of the supply of chlorine - 200 g.

Example 3. The process is carried out as in example 1, except for the supply of chlorine - 260 g.

Example 4. The process is carried out as in example 1, except for the supply of the complex - 0.03 g.

Example 5. The process is carried out as in example 1, with the exception of the supply of chlorine - 100 g.

Example 6. The process is carried out as in example 1, with the exception of the reaction time of 100 minutes

Example 7. The laboratory mixer is loaded, in g: PVC resin - 356, dioctyl phthalate - 39, asbestos 377, ΤίΟ ₂ - 36, stearate-Ca - 4, pigment - 1 and chloroplast-300 - 156, the resulting mixture to obtain linoleum samples passed through laboratory rollers at 140 ° C, the rolling time of 8-10 minutes

After processing the polyvinyl chloride composition, the resulting linoleum is subjected to a laboratory test for absolute and permanent deformation, abrasion and linear dimensions.

The test results are presented in table. 2.

Example 8. The process is carried out as in example 7, except for the supply of dioctyl phthalate - 19 g and chloroplast-300 - 176 g.

Example 9. The process is carried out as in example 7, with the exception of the supply of chloroplast-300 - 195,

Example 10. The process is carried out as in example 7, with the exception of the supply of chloroplast-300 - 213,

Example 11. The process is carried out as in example 7, with the exception of the supply of chloroplast-300 - 242,

Example 12. The process is carried out as in example 7, with the exception of the supply of chloroplast-300 - 264,

Example 13. The process is carried out as in example 7, with the exception of the supply of chloroplast-300 - 300 g.

The proposed method of chlorinating a mixture of C ₁₀ -C ₁₆ n-paraffins and C ₁₀ -C ₁₆ alkylbenzenes with the content of iron ions, using ethylene diamine-L1-dimethylphosphonic acid as a complexon, allows the process to be carried out at 100-105 ° C with the exception of the formation of FeCl3 and the implementation of chlorination in the side chain of alkylbenzenes.

Received a clear liquid chloroplast-300 with a color on an iodometric scale of 12-20 units. Chloroplast-300 compared with phthalic plasticizers is 20 times less toxic and MPC is 10 mg / m ³ .

In the composition of the PVC composition for producing linoleum, the amount of plasticizer used is 20.12 wt.%. From the experiments (see table. 2) it is clear that when replacing the specified amount of plasticizer with chloroplast-300 (experiments No. 9, 10), all indicators of linoleum comply with GOST except for a sharp increase in brittleness and lower frost resistance. A further increase in the amount of chloroplast-300 in the composition of the PVC composition to 25-27 wt.% Reduces brittleness and increases the frost resistance of linoleum, all indicators comply with the requirements of regulatory and technical documentation.

It should be noted that the presence of a polarizable benzene group and a sufficient amount of polar groups (chlorine) in the composition of chloroplast-300 increases the overall polarity of the plasticizer and

- 2 013124 capacity with polyvinyl chloride resin.

According to the order of the USSR State Planning Commission from 1985-1990. carried out industrial tests of the chloroplast plasticizer in the production of linoleum and polyvinyl chloride gross. The tests were carried out in the cities of Liepaja, Odessa, Kiev, Sumgait, Angarsk, Hlyupin, Moscow Region. Industrial testing of chloroplast as a plasticizer of the PVC composition makes it possible to replace up to 70-75% of dioctyl phthalate with chloroplasts.

Table 1

I

L " Name of components Results and numbers of experiments one 2 3 4 5 6 I Taken: A mixture of C ₁₀ -C | b n-paraffins -76% and Syu-C | ₆ alkylbenzenes-24% F 150 150 150 150 150 150 2 Evaporated chlorine gr 150 200 260 150 one hundred 150 3 Complexon-ethylenediamine-Ν, Ν ^1- dimethyl phosphonic acid, gr 0.015 0.015 0.015 0,03 0.015 0.015 4 Temperature, ° C 105 105 105 one hundred 120 105 5 Reaction time, min 120 120 120 120 120 one hundred 6 Obtained: a mixture of chlorinated C-Cu _w n-paraffins and Hsiu-Cn, alkyl benzenes gr 226 248 278 226.5 200 200.5 Epoxy resin to stabilize the final product 2 mass. % gr 4,5 5,0 5.6 4,5 4.0 4.0 The content of bound chlorine in the composition of the final product,% 33.0 40,0 46.0 33.5 25.0 25.5 10 Exit, % 98.7 99.1 99,2 98.9 98.5 90.6 ί

table 2

.one" Name of components Numbers and results of experiments GOST 14682-79 7 8 nine 10 eleven 12 thirteen one Taken: Paul ive and n ilchloride, ^G R 356 356 356 356 356 356 356 356 2 Dioctyl Phthalate ^G R 39 nineteen - - - 130 3 Chloroparaffin HP-470, N> - - - - 65 4 Asbestos, gr 377 .'77 377 359 330 308 272 377 5 _{2 by} . GR 36 36 36 36 36 36 36 36 6 Stearate Sa gr 4 4 4 4 4 4 4 4 7 Pigment, gr one one one one one one one one 8 "Chloroplast-300." gr 156 176 195 213 242 264 300 - nine Indicators of the obtained linoleum: Absolute deformation 0.60 0.40 0.19 0.20 0.20 0.14 0.19 0.60 10 Absolute residual strain <0.22 <>. 20 <0.10 <0.15 <0.10 <0.18 <0.20 <0.25 eleven Linear Resizing % 50,5 > .a40 <0.35 <0.30 <0.32 <0.30 <0.40 <0.5 12 Abrasion, MKM <120 <80 <56 <50 <50 <48 <120 thirteen Colour l and m about n n s th 14 Thickness. mm 1.5 . 5 1.8 1.5 1,5 1.5 1,5 1.5 fifteen Fragility the norms the norms crunch crunch the norms the norms

Literature

1. Zalimova M.M., Rakhimkulova A.A., Rakhmatullina F.Kh. Environmental technologies in oil refining and petrochemicals. Materials of the Scientific and Practical Conference, Ufa, October 8 2003 and Reports of the Industrial Ecology Meeting. Moscow, June 5, 2003, Ufa. Inkhp Publishing House, 2003. 128-129. Rus

2. Auth. testimonial. 1401818 USSR, MKI ³ S 07C 21/24; 17/14, 02/08/1988

3. Autosvid. 1112026 USSR, MKI ³ S 07C 19/02; 17/10, dated May 08, 1984

Claims (1)

A method of producing a chlorohydrocarbon plasticizer of polyvinylchloride linoleum by chlorination of hydrocarbon raw materials at 100-120 ° C in the presence of complexon based on acetic acid and aniline, characterized in that to replace the expensive phthalic plasticizer and improve the physicomechanical properties of polyvinyl chloride linoleum, a mixture is used as a hydrocarbon feed the residue of distillation of reverse paraffin containing, wt.%: C ₁₀ -C ₁₆ n-paraffins 76-80 and C1 ₀ -C _{6 6} -alkylbenzenes 20-24, as a complexone ethyl ndiamine-ΝιΝ ¹ - 3 013124 dimethylphosphonic acid, taken in an amount of 0.015-0.03 wt.% By weight of the feedstock, and the chlorination process is carried out at a mass ratio of a mixture of hydrocarbons and chlorine equal to 1: 1-1.8, at a temperature of 100-105 ° C .