DE2411445C3 - Process for the production of hydrocarbon resins by pressure-heat polymerization of mixtures containing C5 diolefin oligomers - Google Patents

Description

The invention relates to a process for the production of hydrocarbon resins with high Softening points by pressure-heat polymerization of mixtures containing Cs-diolefin oligomers in an oxygen-free atmosphere at a temperature of 260 - 310 ° C

It is known from the literature that in Q fractions, the diolefins, such as isoprene, cis- and trans-piperylene and Contain cyclopentadiene, the diolefins when subjected to pressure and heat treatment di-, tri- or tetramerize (see US Pat. No. 3,290,275).

By thermal aftertreatment 300-330 ⁰ C can be prepared from the oligomeric Cs diolefin polymers having softening points of up to 27 ° C obtained (see. US-PS 32 90 275). On the other hand, it has not been possible so far. To produce resins with a high softening point thermally from Cs diolefins.

The invention is based on the object of a method for the production of light, heat and oleoreactive hydrocarbon resins with high softening points through pressure-heat polymerization of mixtures containing Cs-diolefin oligomers in an oxygen-free atmosphere.

The object of the invention is achieved in that a mixture of 5 to 95 wt .-% of a previously of the low-boiling, non-resinous fractions freed oligomer mixture from the boiling range from 150 to 390 ° C and 95 to 5 wt .-% dicyclopentadiene at the specified temperature and a pressure of 4 to 12 atü for at least 4 hours.

It is already known that during the polymerization of petroleum hydrocarbon fractions by adding dicyclopentadiene an increase in the Softening point of the resins obtained can be achieved (cf. z. B. FR-PS 11 02 842). The thermal However, polymerization in the process of the invention takes place in a temperature range where dicyclopentadiene (DCPD) has already been split into cyclopentadiene (CPD), and the circumstances are therefore very different from in the process according to FR-PS 1102 842, in which DCPD is added, but the polymerization in one Temperature range takes place where DCPD has not yet split into CPD.

The knowledge of the person skilled in the art that the thermal polymerization in the temperature range of the cleavage of DCPD takes place in CPD, but also had to hold him back from using DCPD to increase the softening point, as it was known from the catalytic process according to the FR-PS, to a thermal polymerization process as to be transferred according to FR-PS 11 02 842; because in the FR-PS it is expressly stated that the Addition of monomers! CPD Leads to Insoluble Resins In the process of the invention, however, Resins just obtained, which are very soluble in toluene

ίο and especially in white spirit.

It has been found that in order to increase the resin softening point it is necessary to separate the oligomer mixture produced by pressure-heat polymerization before further polymerization from the low-boiling, non-resinable components, since these act like a solvent. In contrast to cationic polymerization, where dilution usually raises the softening point, a solvent has the effect of lowering the softening point in thermal polymerization. The separation of all constituents which boil up to a sump temperature of 150 ° C. proved to be beneficial. After this treatment, the oligomer has the boiling point at 150 ° C and the final boiling point at 380 to 390 ⁰ C.

When this Oligomerenkonzentrat atm in pressure vessels within 3 to 18 hours at 4 to 12 and polymerization temperatures between 300 and 325 ° C and is worked up by the polymer by steam distillation (up to 280 ⁰ C), but can only resins with

jo softening points of up to 60 ° C can be generated. Also at a longer reaction time is not possible

To raise softening point significantly when than Feedstock only Cs oligomer is used. Only by adding DCPD to the Cs oligomer

concentrate it is by the invention

Process possible using reactive and readily soluble resins Targeted softening points between 60 and 140 ° C

to manufacture.

In contrast to resins made from pure DCPD or

Resins made from DCPD-Cs oligomer mixtures have pure Cs oligomerizate significantly improved solubility properties in toluene and especially in white spirit.

However, it has been found that the

Polymerization of a mixture of dicyclopentadiene and oligomer concentrate the reaction temperature and the reaction time must be carefully observed. If the reaction temperature is too high, dark resins are formed. If the reaction temperature is too low, resins that are difficult to dissolve are formed. If the reaction time is too short, poorly soluble resins are also formed. As well suited to Reaklionstemperaturen proven to 260-310 ⁰ C and reaction times of about 4 hours. In the case of high concentrations of Cs oligomer, the temperature chosen is higher; in the case of high concentrations of DCPD, the temperature is chosen to be lower. The oligomer concentrate and DCPD are polymerizable in all proportions. However, if the concentration of DCPD is over

M) rises 70%, the Reaction temperature maintained b / w. the heat of reaction be quickly discharged. It has been shown that at such high concentrations of DCPD a Solvents (e.g. xylene) favor the reaction

bi influenced. In this case, further Extend the reaction time even in the presence of a solvent that is soluble in toluene and white spirit Resin can be obtained.

Process for the production of the Oligomerekonzentraites Procedure I.

A mixture of n-pentane 0.2%. Pentene (2) 0,!)%, Isoprene 19.7%, 2-methyl-butene (2) 3.7%, trans-piperylene 27.7%, cis-piperylene 16.3%, cyclopentadiene 3, 1%, methyl pentenes 12%, dicyclopentadiene 14.6%, and • unidentified proportions 1.8% is continuously pumped through a jacket-heated reaction tube. In the reaction tube the mixture at a pressure of 60 atm is at 320 ° C heated After a residence time of 45 min, the mixture leaves the reactor and passes through a heated at 160 ⁰ C thin film evaporator. In this way, the low-boiling components are separated The Oligomerengemtsch immediately from the oligomers then the initial boiling point at 150 ° C and the final boiling point at 380 to 390 ⁰ C and a bromine number between 150 and 200. Relative to the feed mixture are weighed approximately 80% oligomer .

Procedure Il

Exactly as in method I, a mixture of the following composition is treated: isopentane 6.1%, no identif. 3.7% 2-methylbutene- (I) 4.6%, n-pentane 163%, cis / trans-pentene 23%, isoprene 193%, 2-methylbutene- (2) 3.4%, trans-piperylene 103%. cis-piperylene 5.9%, cis-2-methylpentene 4.0%, trans-2-methylpentene 53%. not identif. 0.7%, benzene 13% and dicyclopentadiene

An oligomer mixture as in process I is obtained in 48% yield.

Procedure III

As in method I, a mixture of the following composition is treated: not identif. 0.4%, Isopentane 7.0%, not identif. 43%. 2-methylbutene- (1) 43%. n-pentane 15.4%, cis / trans-pentene- (2) 3.4%, isoprene 16.1%, 2-methylbutene- (2) 2.1%, cis / trans-2-Me-

Tabel

ethylpentene- (3) 12.0%, not identif. 2.4%, benzene 3.4% and dicyclopentadiene 14.7%.

An oligomer mixture with a bromine number of 177 is obtained in 40% yield.

The comparative test results compared in the table below show the advantages of the procedure according to the invention. The comparison tests ac show that no polymers having softening points (EP) are formed substantially at the pressure-Warm * .- polymerization of mixtures of Cs-oligomers without DCPD addition over 60 ⁰ C.

Examples 1 to 4 show that, with the procedure according to the invention, polymers with softening points from 70 to 139 ° C which are clear in toluene or white spirit are soluble. The comparative experiments D and E also show that with reaction times of less than 4 hours (here 3 hours) no polymers are formed in toluene or in white spirit are clearly soluble ("I" or "II" in the 2nd column of the table means: oligomer from method I or II).

Comparative tests A to C

The oligomer concentrate is heated in an oxygen-free atmosphere in a pressure vessel ^{filled to 2} liters. After the reaction has ended, the low molecular weight components are separated off by steam distillation. Results and reaction conditions are shown in the table

Examples 1 to 4

As described in comparative experiments A to C, mixtures of DCPD and Cs oligomer concentrate are used Treated test results and reaction conditions are recorded in the table The used Dicyclopentadiene was 873% and contained 3.1% unknowns as accompanying components. 43% benzene, 1.8% Cyclopentadiene and 3.1% Cs hydrocarbons.

Oligomer
Parts by weight 1500 additive
Parts by weight Temp.
C. Time
H pressure
atü solubility
Toluene test
petrol clear EP
C. Bromine. Steam
distillation
to C Comparison
attempt A I. 1500 - 325 8th 9.3 clear clear 41 78 280 Comparison
attempt B I. 1500 - 320 18th 8.6 clear clear 62 67 280 Comparison
try C I. 1200 - 315 10 9.6 clear clear 55 72 280 Example I. II 450 DCPD 300 310 6th 8.5 clear clear 70 64 240 Example 2 II 450 DCPD 1050 260 6th 6.1 clear clear 117 62 240 Example 3 II 300 DCPD 1050 270 6th 6.2 clear clear 127 61 240 Example 4 I. 900 DCPD 1200 260 6th 5.6 clear cloudy 139 60.5 240 Comparison »
try D I. 750 DCPD 600 270 3 6.2 cloudy cloudy 65 99 240 Comparison
try I. DCPD 750 270 3 5.2 cloudy 66 75 240

Claims (1)

Claim: Process for the preparation of hydrocarbon resins by pressure-heat polymerization of mixtures containing Cs-diolefin oligomers in an oxygen-free atmosphere at a temperature of 260 to 310 ° C, characterized in that a mixture of 5 to 95 wt .-% of a previously of the low-boiling, non-resinous fractions of freed oligomer mixture from the boiling range of 150 to 390 ⁰ C and 95 to 5 wt .-% dicyclopentadiene exposed to the specified temperature and a pressure of 4 to 12 atmospheres for at least 4 hours