RU2218358C1 - Method for production of petroleum polymer resins - Google Patents

Abstract

FIELD: polymer production. SUBSTANCE: petroleum polymer resins are prepared by catalytic polymerization of unsaturated compounds of liquid product fraction obtained from pyrolysis of straight-run gasolines with boiling range 130-190 C, after which catalyst is neutralized by 1,20epoxy compounds having general formula:

, wherein R is CH₂-O-R′,, R' is C_nH_2n+1 (n= 1-5). cyclohexyl, or C₆H₅R″, in which R" is hydrogen, methyl, ethyl, n- and iso-propyl, tert-butyl, Cl, Br, methoxy, or ethoxy group, in stoichiometric amount to summary number of chlorine atoms and alkyl substituents in selected catalytic system. Neutralization products remain in petroleum polymer resin composition. EFFECT: simplified catalyst neutralization step and improved environmental condition thanks to reduced amount of waste water and solid slimes. 4 tbl

Description

 The invention relates to a method for producing petroleum polymer resins (NPS) - substitutes for expensive and scarce products of natural origin: vegetable oils (in paints and varnishes), rosin (in paper production), as well as wood-pyrogenic and indene-coumarone resins (in rubber compounds and production rubber products).

Known methods for producing NPS from fractions of liquid pyrolysis products of ionic and radical polymerization. The disadvantages of the method of radical polymerization are the necessity of carrying out the process in harsh conditions: 250 ^o C, 11.5 atm, 3.5 hours [USSR AS 717081. A method for producing a petroleum polymer resin. Varshaver E.M. et al., publ. 02.25.80] or longer reaction time: 15 hours at 160 ^{° C.} [USSR AS 861356. A method for producing a petroleum polymer resin. Aliev S.M., publ. BI 1981, 33].

Closest to the proposed is the method of ionic polymerization. Known methods of polymerization of various unsaturated fractions of liquid pyrolysis products under the action of aluminum chloride and its complexes at 60 ^o [Japanese Application 57-195715. A method of producing petroleum resins, publ. 1.12.82] and under the action of catalytic systems consisting of titanium tetrachloride and organoaluminum compounds [RF Patent 2079514. A method for producing petroleum polymer resins. Sukhikh G.L., Bondaletov V.G., Mareychev V.M., publ. 05.20.97, BI 14]. In these cases, polymerization proceeds under milder conditions, but also has drawbacks. One of the main disadvantages is the stage of neutralization when using aqueous solutions of alkalis and ammonia. At the same time, they are mandatory
- separation of the aqueous and organic phases by settling, often associated with preliminary dilution of the reaction mass due to its high viscosity;
- centrifugation to separate titanium and aluminum hydroxides and partially water;
- drying by azeotropic distillation of water with its subsequent separation from unreacted hydrocarbons.

 The objective of the invention is to simplify the technology for the production of NPS, eliminate the noted drawbacks, improve the environmental friendliness of the process by reducing the amount of wastewater and solid sludge and reduce the cost of polymerization products.

где R - H; С_nН_2n+1 (n=1-3); CH₂-О-R', где R' - C_nH_2n+1 (n=1-5), С₆Н₁₁ (циклогексил); C₆H₅R", где R" - H, СН₃, С₂Н₅; н- и изо-С₃Н₇, н-, изо- и трет-С₄Н₉, Сl, Вr, ОСН₃, ОС₂Н₅.The problem is solved by using 1,2-epoxy compounds of the general formula as catalyst neutralizing reagents

where R is H; With _n H _{2n + 1} (n = 1-3); CH ₂ —O — R ′, where R ′ is C _n H _{2n + 1} (n = 1-5), C ₆ H ₁₁ (cyclohexyl); C ₆ H ₅ R ", where R" is H, CH ₃ , C ₂ H ₅ ; n- and iso-C ₃ H ₇ , n-, iso- and tert-C ₄ H ₉ , Cl, Br, OCH ₃ , OC ₂ H ₅ .

Using the proposed method allows you to:
1. Avoid the use of caustic alkali solutions.

 2. To reduce the applied excess of the used neutralizing agent due to the homogeneity of the neutralization process.

 3. Eliminate the stages of sedimentation, centrifugation and drying.

 4. To reduce the time of the stage of neutralization of the catalyst.

 5. Dispose of wastewater and solid sludge.

 6. Improve the environmental situation in the workplace.

 7. Reduce the cost of the resulting product.

 Example 1

To a round bottom flask with an anchor stirrer is charged with 250 g of liquid products of pyrolysis fractions from straight-run gasoline boiling range 130-190 ^o C. At a temperature of 35-40 ^o C with the stirrer operating in a flask charged with 3.75 g of aluminum chloride powder, and then the temperature in the reactor increase to 80-85 ^o C and at this temperature the reaction mass is stirred for 3 hours. At the end of this time, the temperature in the reactor is reduced to 30-35 ^o C and when the stirrer is dosed, 7.4 g of glycidol methyl ester is dosed. The reaction mass is stirred with a gradual increase in temperature to 90 ^o With the complete disappearance of the brown color of the reaction mass and obtain a clear solution. Then from the flask at a temperature of 190-200 ^o C and a residual pressure of 5 mm RT. Art. unreacted hydrocarbons are distilled off. The resin yield is 135 g, which is 54% by weight, based on the starting fraction. The softening point of 94 ^o C RuNO color 300 mg I _2/100 ml, an acid number of 0.4 mg KOH / g, iodine number 48.1 g I _2/100 g

 Example 2

To a round bottom flask with an anchor stirrer is charged with 250 g of a fraction of liquid pyrolysis products from straight-run gasoline boiling range 130-190 ^o C. At a temperature of 35-40 ^o C at the reactor operating mixer is charged with 5 g of titanium tetrachloride, and then at 60 ^o C is charged 3 g of triethylaluminum (TEA) as a 20% solution in heptane. After loading the catalytic complex, the temperature in the reactor was raised to 80-85 ^o C and the reaction mass was stirred for 4 hours. At the end of this time, the temperature in the reactor is reduced to 30-35 ^o C and for 0.5 hours with a working stirrer serves 16.2 g of glycidol methyl ester. Then the temperature is gradually increased to 80-90 ^o C and the reaction mass is stirred until the brown color of the reaction mass completely disappears and a clear solution is obtained. Then from the reactor at a temperature of 190-200 ^o C and a residual pressure of 5 mm RT. Art. unreacted hydrocarbons are distilled off. The resin yield is 130 g, which is 52 wt.% In terms of the initial fraction. The softening temperature of RuNO 88 ^o C, the color of 50 mg I _2/100 ml, an acid number of 0.2 mg KOH / g, iodine number 49.6 g I _2/100 g

 Example 3

To a round bottom flask with an anchor stirrer is charged with 250 g of a fraction of liquid pyrolysis products from straight-run gasoline boiling range 130-190 ^o C. At a temperature of 35-40 ^o C at the reactor operating mixer is charged with 5 g of titanium tetrachloride, and then at 60 ^o C is charged 3.2 g of diethylaluminium chloride (DEAC) as a 20% solution in heptane. After loading the catalytic complex, the temperature in the reactor was raised to 80-85 ^o C and the reaction mass was stirred for 4 hours. At the end of this time, the temperature in the reactor is reduced to 30-35 ^o C and for 0.5 hours with a working stirrer serves 16.1 g of glycidol methyl ester. Then the temperature is gradually increased to 80-90 ^o C and the reaction mass is stirred until the brown color of the reaction mass completely disappears and a clear solution is obtained. Then from the reactor at a temperature of 190-200 ^o C and a residual pressure of 5 mm RT. Art. unreacted hydrocarbons are distilled off. The resin yield is 130.4 g, which is 51 wt.% In terms of the initial fraction. The softening temperature of RuNO 91 ^o C, the color of 60 mg I _2/100 ml, an acid number of 0.15 mg KOH / g, iodine number 51.2 g I _2/100 g

 Examples of the synthesis of oil-polymer resins using aluminum chloride as a catalyst are shown in table 1.

 Examples of the synthesis of petroleum polymer resins using titanium tetrachloride as a catalyst and as cocatalysts of triethyl aluminum, diethyl aluminum chloride and triisobutyl aluminum are shown in tables 2, 3 and 4, respectively.

Catalyst neutralizers (glycidyl ethers) were synthesized according to the methods [Sorokin M.F., Lyalyushko K.A. Workshop on chemistry and technology of film-forming substances. M.: Chemistry, 1971, 264 pp.] And [Shvets V.F., Lebedev N.N. Kinetka and catalysis, 1963, vol. XLII, p. 360]. Glycidyl ethers are introduced into the reaction medium containing up to 50% unreacted hydrocarbons in bulk, since the esters used, in addition to the methoxyphenol glycidyl ether ( _mp = 36 ^° C), are liquids. Catalyst deactivation products remain in the composition of petroleum resins.

Claims (1)

The method of producing oil-polymer resins by polymerization of unsaturated compounds of the fraction of liquid pyrolysis products of straight-run gasolines with boiling limits of 130-190 ° C in the presence of catalytic catalysts - aluminum chloride, titanium tetrachloride and organoaluminum compounds in molar ratios: TiCl ₄ : Al (C ₂ H ₅ ) ₂ Cl = 1: (0.1-10); TiCl ₄ : Al (C ₂ H ₅ ) ₃ = 1: (0.1-10); TiCl ₄ : Al (iso-C ₄ H ₉ ) ₃ = 1: (0.1-10), characterized in that the neutralization of the catalyst is carried out by 1.2 epoxy compounds of the General formula

where R is CH ₂ -O-R ', where R'-C _n H _{2n + 1} (n = 1-5), C ₆ H ₁₁ (cyclohexyl); C ₆ H ₅ R ", where R '' is H, CH ₃ , C ₂ H ₅ , n- and iso-C ₃ H ₇ , n-, iso and t-C ₄ H ₉ , C1, Br, OCH ₃ , OS ₂ H ₅ , in the amount stoichiometric to the total number of chlorine atoms and alkyl substituents at the aluminum and titanium atoms in the selected catalytic system, while the neutralization products remain in the composition of oil-polymer resins.

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