RU2359977C1 - Method for preparation of modified petroleum polymer gums - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to polymer technology, precisely to method for preparation of petroleum polymer gums. The method for preparation of modified petroleum polymer gums is described. It comprises polymerisation of unsatisfied compounds of liquid products fractions of straight run gasoline pyrolysis with range of boiling from 130 to 190°C and alkyl metacrylates characterised in that polymerisation is carried out at 60-80°C within 60-120 minutes in the presence of catalyst systems - titanium tetrachloride and organoaluminium at the following mole ratio: TiCl₄ : Al(C₂H₅)₂Cl=1:(0.1÷3); TiCl₄:Al(C₂H₅)₃=1:(0.1÷3); TiCl₄: Al(iso-C₄H₉)₃=1:(0.1÷3), and 1-2% concentration of TiCl₄ in catalyst complex with further inactivation of catalyst complex with propylene oxide.

EFFECT: reduction of durance and time of process, increase of gums yield.

1 cl, 3 tbl, 3 ex

Description

The invention relates to the technology of low molecular weight polymer compounds, and in particular to a method for producing petroleum polymer resins that are used in various industries: paint, varnish, tire, printing, for the production of varnish, sealants, adhesives, various filled compositions, as substitutes for expensive vegetable oils.

A known method of producing petroleum polymer resins (NPS) [RF Patent No. 2079514. IPC ⁶ C08F 240/00. Publ. 05/20/97. Bull. No. 14] by polymerization of unsaturated hydrocarbons, fractions of liquid gasoline pyrolysis products with a boiling point of 130 to 190 ° C in the presence of Ziegler-Natta catalysts based on titanium tetrachloride (TXT) and organoaluminum compounds (AOS): diethylaluminium chloride (DEAC), triethylaluminum (TEA) and triisobutylaluminum (CHIBA). Improving the quality indicators of the NPS, as well as their operational characteristics, can be achieved by modifying the NPS, and modification is possible both of the feedstock (fractions of the liquid pyrolysis products) and the oil-polymer resins proper.

A known modification of the actual oil-polymer resins with maleic anhydride [RF Patent No. 2177959. IPC ⁷ C08F 240/00, 8/46. Publ. 01/10/02. Bull. No. 1], which consists in the interaction of NPS with maleic anhydride at a temperature of 120-150 ° C in the presence of organoaluminum compounds: DEAC, TEA. The need for preliminary obtaining the initial NPS, its separation from the reaction mass and drying before subsequent modification makes it difficult to use this method of obtaining a modified resin.

Closest to the proposed one is a method for producing modified oil-polymer resins by polymerization of methacrylic acid (MMA) modified with methyl ether, a feedstock - a fraction of the liquid pyrolysis products boiling at a temperature of 130 to 190 ° C [Shikhalizade PD, Aliev SM, Mehtiyev S.I., Muradova M.O. // Azerb. Chem. Journal. - 1977. - No. 3. - p. 58-50]. The disadvantages of this process are the high temperature (not lower than 120 ° C), the presence of a peroxide initiator (isopropylbenzene hydroperoxide), a significant duration of the process (20-30 hours), while the yield per feedstock is from 26.2 to 27.4% .

The objective of the invention is to simplify the technology for producing modified petroleum polymer resins: reducing the duration and temperature of the process, increasing the yield of resins.

The problem is solved by polymerization of unsaturated compounds of the fraction of liquid pyrolysis products of straight-run gasoline with boiling ranges from 130 to 190 ° C and alkyl methacrylate (alkyl: methyl, butyl, hexyl), taken in an amount of 5 to 20%, under the action of catalytic systems titanium tetrachloride - organoaluminum compound in molar ratios:

TiCl ₄ : Al (C ₂ H ₅ ) ₂ Cl = 1: (0.1 ÷ 3);

TiCl ₄ : Al (C ₂ H ₅ ) 3 = 1: (0.1 ÷ 3);

TiCl ₄ : Al (iso-C ₄ H ₉ ) ₃ = 1: (0.1 ÷ 3),

and a concentration of TiCl ₄ in the catalytic complex of 1-2%, at a temperature of 60-80 ° C and a reaction time of 60-120 minutes, followed by deactivation of the catalytic complex with propylene oxide. The reaction products of the catalytic complex with propylene oxide remain in the composition of the obtained resin.

Using the proposed method allows you to:

1. to carry out the reaction at a low temperature (60-80 ° C),

2. significantly reduce the duration of the process compared to the radical process (10-20 times);

3. increase the yield of resin by 1.5-1.8 times.

Table 1 presents the results of the polymerization of the methyl methacrylate fraction in the presence of various catalytic systems.

Table 2 presents the results of the polymerization of the fraction and butyl methacrylate in the presence of various catalytic systems.

Table 3 presents the results of the polymerization of the fraction and hexyl methacrylate in the presence of various catalytic systems.

The amount of alkyl methacrylate introduced varies from 5 to 20%, since the improvement in properties is not proportional to the amount of alkyl methacrylate introduced: a decrease in the content below 5% practically does not improve the properties of the NPS, and with the introduction of alkyl methacrylate above 20%, the improvement in properties becomes insignificant and, therefore, economically unreasonable.

The proposed method for producing modified NPS by polymerizing fractions with boiling ranges from 130 to 190 ° C (91%) and methyl methacrylate (9%) under the influence of various catalytic systems (the molar ratio of the components of the catalyst system TXT and AOS 1: 0.3) is confirmed by examples.

Example 1

150 g of a fraction of the liquid pyrolysis products of straight-run gasoline with boiling limits from 130 to 190 ° C and 15 g of methyl methacrylate are loaded into the reactor with an anchor stirrer. With the stirrer operating, 17.5 g (10.17 ml) of titanium tetrachloride and 0.57 g (3.85 ml) of triethylaluminum (TEA) are loaded into the reactor as a solution in heptane (TEA concentration in heptane 0.148 g / ml, molar ratio TiCl ₄ : (C ₂ H ₅ ) ₃ Al = 1: 0.3) at a temperature of 20 ° C. After loading the catalytic complex, the temperature was raised to 80 ° C and the reaction mixture was stirred for 60 minutes, then 24.5 g (28.6 ml) of propylene oxide taken with a 10% excess were fed into the reactor, and the reaction mixture was stirred until the brown disappeared completely coloring the reaction mass and obtaining a clear solution. Then from the reactor at a temperature of 190-200 ° C and a residual pressure of 5 mm RT.article unreacted hydrocarbons are distilled off. The resin yield of 69.3 g, which is 42% based on the loaded raw materials. RuNO softening temperature 111 ° C, color of 10% resin solution in xylene 130 mg I _2/100 ml, the iodine number 61.6 g I _2/100 g

Example 2

150 g of a fraction of the liquid pyrolysis products of straight-run gasoline with boiling limits from 130 to 190 ° C and 15 g of methyl methacrylate are loaded into the reactor with an anchor stirrer. With the stirrer operating, 17.5 g (10.17 ml) of titanium tetrachloride and 0.62 g (3.15 ml) of diethylaluminium chloride (DEAC) are loaded in the form of a solution in heptane (the concentration of DEAC in heptane is 0.199 g / ml, molar ratio TiCl ₄ : (C ₂ H ₅ ) ₂ AlCl = 1: 0.3) at a temperature of 20 ° C. After loading the catalytic complex, the temperature was raised to 80 ° C and the reaction mixture was stirred for 60 minutes, then 24.5 g (28.6 ml) of propylene oxide taken with a 10% excess were fed into the reactor, and the reaction mixture was stirred until the brown disappeared completely coloring the reaction mass and obtaining a clear solution. Then from the reactor at a temperature of 190-200 ° C and a residual pressure of 5 mm RT.article unreacted hydrocarbons are distilled off. The resin yield of 70.9 g, which is 43% based on the loaded raw materials. RuNO softening temperature of 110 ° C color 10% resin solution in xylene 130 mg I _2/100 ml, the iodine number 63.2 g I _2/100 g

Example 3

150 g of a fraction of the liquid pyrolysis products of straight-run gasoline with boiling limits from 130 to 190 ° C and 15 g of methyl methacrylate are loaded into the reactor with an anchor stirrer. With the stirrer operating, 17.5 g (10.17 ml) of titanium tetrachloride and 0.99 g (6.6 ml) of triisobutylaluminum (TIBA) are loaded in the form of a solution in heptane (the concentration of TIBA in heptane is 0.150 g / ml, molar ratio TiCl ₄ : (C ₄ H ₉ ) ₃ Al = 1: 0.3) at a temperature of 20 ° C. After loading the catalytic complex, the temperature was raised to 80 ° C and the reaction mixture was stirred for 60 minutes, then 24.5 g (28.6 ml) of propylene oxide taken with a 10% excess were fed into the reactor, and the reaction mixture was stirred until the brown disappeared completely coloring the reaction mass and obtaining a clear solution. Then from the reactor at a temperature of 190-200 ° C and a residual pressure of 5 mm RT.article unreacted hydrocarbons are distilled off. The resin yield of 66.0 g, which is 40% based on the loaded raw materials. RuNO softening temperature of 109 ° C color 10% resin solution in xylene 130 mg I _2/100 ml, an iodine number of 64.8 g I _2/100 g

All subsequent syntheses were performed according to a similar procedure. Yield and properties of petroleum polymer resins obtained by polymerization of the fraction of liquid pyrolysis products of straight-run gasolines with boiling ranges from 130 to 190 ° C and methyl methacrylate (butyl methacrylate, hexyl methacrylate) using titanium tetrachloride and triethylaluminium chloride aluminum tri-co-catalysts with different ratios of triisomethyl aluminum chloride components of the catalytic complex, various contents of alkyl methacrylate are shown in tables 1, 2, 3.

Thus, analyzing the data presented in the tables, we can conclude that the polymerization of the modified alkyl methacrylate fraction of the liquid pyrolysis products in the presence of catalyst systems based on TXT and AOS leads to the production of modified NPS with a higher yield compared to the prototype, while the reaction time decreases 10-20 times, and the process temperature is 1.5 times.

Table 1
Synthesis conditions and properties of methyl-methacrylate-modified oil-polymer resins and films based on them Fraction,% Alkyl Acrylate,% Catalytic complex The duration of the reaction, min The reaction temperature, ° C The output of the NPS,% T _posted (RuNO), ° C Iodine number, g I _2/100 g Adhesion score Elasticity, mm Color by iodometry scale mg I _2/100 ml TiCl ₄ ,% Cocatalyst The molar ratio of the components is catalytic. complex Prototype 95 5 Isopropylbenzene hydroperoxide, 0.5% 1200 120 26.2 125 - - - - 91 9 2 (C ₂ H ₅ ) ₂
AlCl 1: 0.1 120 80 41.5 108 61.7 2 10 130 91 9 2 1: 0.3 60 80 43.0 110 63,2 2 10 130 91 9 2 1: 1,0 60 80 42.8 110 63.0 2 10 130 91 9 2 1: 3.0 120 80 43.5 108 64,2 2 10 130 91 9 one 1: 0.3 120 80 43.8 108 62.6 2 10 130 80 twenty 2 1: 0.3 60 80 47.0 118 58.5 one 10 160 91 9 2 1: 0.3 120 60 42,2 110 62.8 2 10 130 91 9 2 (C ₂ H ₅ ) ₃ Al 1: 0.1 120 80 41.0 107 62.0 2 10 130 91 9 2 1: 0.3 60 80 42.0 111 61.6 2 10 130 91 9 2 1: 1,0 60 80 42,4 110 61.8 2 10 130 91 9 2 1: 3.0 120 80 43.0 110 61.8 2 10 130 91 9 one 1: 0.3 120 80 41.0 108 61.0 2 10 130 80 twenty 2 1: 0.3 60 80 48.0 116 64.8 one 10 160 91 9 2 1: 0.3 120 60 42.8 110 61.5 2 10 130 91 9 2 (i-C ₄ H ₉ ) ₃ Al 1: 0.1 120 80 39.2 108 62,4 2 10 130 91 9 2 1: 0.3 60 80 40,0 109 64.8 2 10 130 91 9 2 1: 1,0 60 80 40.5 109 63.8 2 10 130 91 9 2 1: 3.0 120 80 40.8 108 63.0 2 10 130 91 9 one 1: 0.3 120 80 41.0 108 63,4 2 10 130 80 twenty 2 1: 0.3 60 80 45.0 117 61.6 one 10 160 91 9 2 1: 0.3 120 60 40,2 109 63.8 2 10 130

table 2
Synthesis conditions and properties of butyl methacrylate-modified oil polymer resins and films based on them Fraction,% Alkyl Acrylate,% Catalytic complex The duration of the reaction, min The reaction temperature, ° C The output of the NPS,% T _posted (RuNO), ° C Iodine number, g I _2/100 D Adhesion score Elasticity, mm Color by iodometry scale mg I _2/100 ml TiCl ₄ ,% Cocatalyst The molar ratio of the components is catalytic. complex Prototype 95 5 Isopropylbenzene hydroperoxide, 0.5% 1200 120 26.2 125 - - - - 91 9 2 (C ₂ H ₅ ) ₂ AlCl 1: 0.1 120 80 41.5 108 60.9 2 10 130 91 9 2 1: 0.3 60 80 42.0 110 61.2 2 10 130 91 9 2 1: 1,0 60 80 41.8 109 62.0 2 10 130 91 9 2 1: 3.0 120 80 41.5 110 62.5 2 10 130 91 9 one 1: 0.3 120 80 42,4 108 60,4 2 10 130 80 twenty 2 1: 0.3 60 80 44.0 108 58.8 one 10 160 91 9 2 1: 0.3 120 60 41.8 109 61.8 2 10 130 91 9 2 (C ₂ H ₅ ) ₃ Al 1: 0.1 120 80 40,2 107 59.8 2 10 130 91 9 2 1: 0.3 60 80 41.0 109 60.6 2 10 130 91 9 2 1: 1,0 60 80 41.5 109 60.8 2 10 130 91 9 2 1: 3.0 120 80 41.1 110 60.7 2 10 130 91 9 one 1: 0.3 120 80 41,4 107 59.9 2 10 130 80 twenty 2 1: 0.3 60 80 42.0 116 60.8 one 10 160 91 9 2 1: 0.3 120 60 41.3 109 61.0 2 10 130 91 9 2 (i-C ₄ H ₉ ) ₃ Al 1: 0.1 120 80 39.5 107 62.0 2 10 130 91 9 2 1: 0.3 60 80 40,0 109 61.8 2 10 130 91 9 2 1: 1,0 60 80 40,2 109 62.0 2 10 130 91 9 2 1: 3.0 120 80 39.8 108 62,4 2 10 130 91 9 one 1: 0.3 120 80 39.5 1108 61,4 2 10 130 80 twenty 2 1: 0.3 60 80 42.0 115 61.6 one 10 160 91 9 2 1: 0.3 120 60 40,4 108 61.7 2 10 130

Table 3 Fraction,% Alkyl Acrylate,% Catalytic complex The duration of the reaction, min The reaction temperature, ° C The output of the NPS,% T _posted (RuNO), ° C Iodine number, g I _2/100 g Adhesion score Elasticity, mm Color by iodometry scale mg I _2/100 ml TiCl ₄ ,% Cocatalyst The molar ratio of the components is catalytic. complex Prototype 95 5 Isopropylbenzene hydroperoxide, 0.5% 1200 120 26.2 125 - - - - 91 9 2 (C ₂ H ₅ ) ₂ AlCl 1: 0.1 120 80 39.1 108 60.0 2 10 130 91 9 2 1: 0.3 60 80 41.0 111 60,2 2 10 130 91 9 2 1: 1,0 60 80 39.8 110 61.2 2 10 130 91 9 2 1: 3.0 120 80 38.9 110 60.8 2 10 130 91 9 one 1: 0.3 120 80 39.5 109 60.1 2 10 130 80 twenty 2 1: 0.3 60 80 42.0 117 58.5 one 10 160 91 9 2 1: 0.3 120 60 40.8 109 60.8 2 10 130 91 9 2 (C ₂ H ₅ ) ₃ Al 1: 0.1 120 80 39,4 109 58.2 2 10 130 91 9 2 1: 0.3 60 80 41.0 110 61.2 2 10 130 91 9 2 1: 1,0 60 80 41.1 109 60,4 2 10 130 91 9 2 1: 3.0 120 80 38.5 109 59,4 2 10 130 91 9 one 1: 0.3 120 80 39.9 108 60.0 2 10 130 80 twenty 2 1: 0.3 60 80 42.0 117 60.7 one 10 160 91 9 2 1: 0.3 120 60 40.8 108 60.7 2 10 130 91 9 2 (i-C ₄ H ₉ ) ₃ Al 1: 0.1 120 80 39.2 107 61.3 2 10 130 91 9 2 1: 0.3 60 80 40,0 109 62.8 2 10 130 91 9 2 1: 1,0 60 80 39.8 109 62,2 2 10 130 91 9 2 1: 3.0 120 80 38,2 108 63,2 2 10 130 91 9 one 1: 0.3 120 80 39,4 108 61.9 2 10 130 80 twenty 2 1: 0.3 60 80 41.0 116 61.1 one 10 160 91 9 2 1: 0.3 120 60 40,2 108 60.9 2 10 130

Claims (1)

A method for producing modified petroleum polymer resins by polymerizing unsaturated compounds of the fraction of liquid pyrolysis products of straight-run gasolines with boiling ranges from 130 to 190 ° C and alkyl methacrylates, characterized in that the polymerization is carried out at a temperature of 60-80 ° C for 60-120 min in the presence of catalytic systems - titanium tetrachloride and organoaluminum compound in molar ratios:
TiCl ₄ : Al (C ₂ H ₅ ) ₂ Cl = 1: (0.1 ÷ 3);
TiCl ₄ : Al (C ₂ H ₅ ) ₃ = 1: (0.1 ÷ 3);
TiCl ₄ : Al (iso-C ₄ H ₉ ) ₃ = 1: (0.1 ÷ 3),
and a concentration of TiCl ₄ in the catalytic complex of 1-2%, followed by deactivation of the catalytic complex with propylene oxide.