JPS63260913A - Manufacture of cyclopentadiene petroleum resin with high softening point - Google Patents

Abstract

PURPOSE:To produce the title petroleum resin with good reproducibility, by reacting a cyclopentadiene with a specific 9C aromatic hydrocarbon, removing an unreacted hydrocarbon from it, and then effecting thermal polymerization. CONSTITUTION:1mol. of a cyclopentadiene and 0.8-0.06mol. of one or more 9C aromatic hydrocarbons selected from an aromatic hydrocarbon (e.g., styrene) having an ethylenically unsaturated bond and indene are thermally copolymerized in the presence or absence of a solvent such as benzene or xylene in an atmosphere of an inert gas at 220-320 deg.C for 0.1-10hr. Then, the pressure in the polymerization system is reduced and, after removal of an unreacted 9C aromatic hydrocarbon and, if desired, a solvent, the thermal polymerization is effected at 150-300 deg.C for 0.5-10hr.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to cyclopentadiene, an aromatic hydrocarbon having an ethylenically unsaturated bond, and one selected from indesi.
The present invention relates to a method for producing a high softening point thermal copolymerized petroleum resin with a C9 aromatic hydrocarbon consisting of at least 1 species. More specifically, 1 mol of cyclopentadiene and 0.8 mol of 09 aromatic hydrocarbon
~0.06 mol was thermally copolymerized in a temperature range of 220 to 320°C, and after removing unregenerated C9 aromatic hydrocarbons, further thermal polymerization was carried out in a temperature range of 150 to 300°C. The present invention relates to a method for producing a characteristically high softening point cyclopentadiene petroleum resin.

Cyclopentagenes-C9 aromatic carbonization/! The copolymerized petroleum resin of 11' element exhibits properties and behavior different from petroleum resins mainly composed of cyclopentadiene, and has a good rubber percentage (
Due to its high viscosity and high viscosity, it has good compatibility with rubber compounding materials, printing ink and paint compounding materials, and polypropylene films, so it is widely used as a compounding material for these materials [or as a raw material for these materials]. It's being used.

(Prior Art) Copolymerized petroleum resins of cyclopentadiene and CO aromatic hydrocarbons can usually be obtained by thermal polymerization or cationic polymerization in the presence of a catalyst.

The thermal copolymerization method of cyclopentadines and 09 aromatic hydrocarbons has long been disclosed in U.S. Patent No. 2.689.232, etc., but these conventional known techniques mainly By introducing C9-based aromatic hydrocarbons, the softening point is lower than that of petroleum resins.
It is difficult to obtain a resin with a high softening point of 0 to 200°C.

However, in general, in fields where such copolymer resins are widely used as compounding materials for printing inks, etc., copolymer resins that have a relatively high softening point and contain a large amount of C9 aromatic hydrocarbons are prized. For this reason, the thermal copolymerization conditions have to be kept for a long time and at high temperatures, resulting in poor working efficiency and labor efficiency during production, which is disadvantageous in that it is uneconomical. Furthermore, since the amount of C9 aromatic hydrocarbons to be blended is limited, there are limits to the improvement of resin properties and the use of these resins is also limited.

(Problems to be Solved) The present inventors have discovered that cyclopentagenes with a high softening point and C9
The present invention was completed as a result of extensive research into a method for economically producing thermal copolymerized petroleum resins of aromatic hydrocarbons and dramatically increasing the amount of C0 aromatic hydrocarbons. .

That is, according to the method of the present invention, a thermal copolymer resin of cyclopentadiene and C9 aromatic hydrocarbon having a softening point of 100° C. or higher, preferably 120° C. or higher can be easily obtained with good reproducibility.

(Means for Solving the Problems) The present invention provides a C9-based aromatic hydrocarbon consisting of one or more types selected from aromatic hydrocarbons having an ethylenically unsaturated bond and indesi per mole of cyclopentadiene. 8
A raw material system containing ~0.06 mol is thermally copolymerized at a temperature range of 220 to 320°C, unrefined C0-based aromatic hydrocarbons are removed from the polymerization liquid, and then thermal polymerization is performed to obtain a high This is a novel method for producing a thermal copolymer resin of cyclopentadiene and C9 aromatic hydrocarbon that has a softening point and can contain a large amount of C5 aromatic hydrocarbon.

The obtained resin can be used as it is for various purposes, but it can also be modified with maleic anhydride and used as a compounding material for printing inks and paints, or it can be catalytically hydrogenated in a conventional manner and incorporated into pressure-sensitive adhesives, polypropylene, etc. It is particularly effectively used as an agent.

The method of the present invention will be explained in detail below.

One of the raw materials used in the present invention is cyclopentadiene, and the cyclopentadiene includes cyclopentadiene, its multimer, or its alkyl substituted product. The cyclopentadines may be used as a mixture, or a cyclopentadiene fraction (CPD fraction) containing 50% by weight or more may be used.

Further, this CPD fraction may contain an olefinic comonomer copolymerizable with these alicyclic dienes. Examples of the olefinic comonomer include aliphatic olefins such as isoprene, piperylene or butadiene, alicyclic olefins such as cyclopentene, or mixtures thereof.

In view of the spirit of the present invention, it is preferable that the concentration of these olefins is low, but it is permissible if the concentration is 10% by weight or less based on cyclopentadiene.

Another raw material used in the present invention is a C0 aromatic hydrocarbon, and the C9 aromatic hydrocarbon includes an aromatic hydrocarbon having an ethylenically unsaturated bond and/or indesi. Examples of the aromatic hydrocarbon having an ethylenically unsaturated bond include styrene, vinyltoluene, α-methylstyrene, and mixtures thereof. It is also possible to use a mixture of indesi and these aromatic hydrocarbons having ethylenically unsaturated bonds as a raw material.In this case, it is industrially better to use the so-called C8 fraction, which is a by-product from steam cracking such as naphtha. is also advantageous. The C0 aromatic hydrocarbon is blended in an amount of 0.8 to 0.06 mol per mol of cyclopentadiene, but when dicyclopentadiene is used as the cyclopentadiene, it is 2 mol, and in the case of tricyclopentadiene. Each is calculated as 3 moles.

The blended raw material system is in the presence or absence of a solvent such as benzene, xylene, n-hexane or kerosene at a temperature range of 220 to 320°C, preferably 240 to 300°C, preferably with an inert gas such as nitrogen gas. 0 under an atmosphere of
．． Thermal copolymerization is carried out at a pressure higher than that capable of maintaining the polymerization system in the liquid phase for 1 to 10 hours, preferably 0.2 to 6 hours. When a solvent is used, it is added so that the amount of the reaction raw material is about 30% by weight. Subsequently, after reducing the pressure of the polymerization system and removing the unreacted aromatic hydrocarbon and, if necessary, the solvent, an additional 15
The temperature is maintained in a temperature range of 0 to 300'C for 0.5 to 10 hours, preferably 0.5 to 6 hours, and further thermal polymerization is carried out under reduced pressure or increased pressure. The series of polymerization reactions may be carried out either continuously or batchwise.

The ratio of cyclopentashevs and aromatic hydrocarbons constituting the thermal copolymer resin obtained in this way was determined by hydrogen-nuclear magnetic resonance ('H-NMR) on the benzene ring. It was determined by the ratio of the number of hydrogens on the norbornene ring and the number of hydrogens on the cyclopentene ring.

(Effect of the invention) Since the method of the present invention distills off the comonomer in the middle of the polymerization reaction, the polymerization time is shortened compared to the conventional technology, and after the comonomer tJ is distilled off, The polymerization can be carried out at a low temperature, the working efficiency and thermal efficiency during production are good, and therefore it is economical. In addition, by continuing polymerization after distilling off the comonomer in the middle of the polymerization reaction, C
Even if the blending ratio of 9-based aromatic hydrocarbons is increased, the softening point does not decrease, so cyclopentadines with high softening points and C9
A petroleum resin thermally copolymerized with an aromatic hydrocarbon is produced. The thermal copolymer resin obtained by the method of the present invention can be used as a compounding material for rubber, a compounding material for printing inks and paints, or a compounding material for printing inks or paints modified with maleic anhydride, phenol resin, etc., or a compounding material for printing inks or paints after hydrogenation. Widely used as adhesives and polypropylene film compounding materials.

(Example) The present invention will be specifically explained below using Examples.

In each example, a conventional known technique for obtaining a resin by removing the solvent and unreacted monomers immediately after the completion of polymerization at a temperature below the polymerization temperature is also described as a comparative example.

In order to clearly contrast the two, conditions were set so that the total thermal polymerization time was approximately the same.

Example 1 A 700M fraction of dicyclopentadiene obtained by steam cracking of naphtha and containing 76.7% by weight of dicyclopentadiene, with the remainder being saturated hydrocarbons, contains 8.4 moles calculated as cyclopentadiene. ) and commercially available α-
300 g (2.5 moles) of methylstyrene (first grade reagent) was charged into a No. 21 autoclave equipped with a stirrer and a spiral tube for heating and cooling, and copolymerized at 270° C. for 3 hours under a nitrogen atmosphere. The pressure at this time was 16.0 Kg/ff1 (G). After the polymerization was completed, the mixture was rapidly cooled and heated at 250° C. for 20 minutes under slight pressure in a nitrogen stream using a rotary evaporator to remove inert fractions and unreacted α-methylstyrene in the raw materials.

Subsequently, oligomers, etc. were removed for 5 minutes at the same temperature in an elementary air flow at 50 TORR, and polymerization was further carried out for 55 minutes under the same conditions.
Copolymer resin 71911 having a softening point of 154°C was obtained.

Comparative Example IA Using the same raw materials as in Example 1, copolymerization was carried out at 270° C. for 4 hours in the same manner. Then 25 in rotary evaporator
Heating at 0℃ for 20 minutes removes inactive fractions and unreacted α-
After removing methylstyrene, it was further heated at the same temperature for 50 minutes in a nitrogen stream.
The mixture was held at TO[tR, for 5 minutes to remove oligomers and the like to obtain copolymer resin 806I having a softening point of 137°C.

Comparative Example IB Copolymer resin 69 with a softening point of 153° C. was prepared in the same manner as Comparative Example IA except that α-methylstyrene whose concentration was adjusted to 63.0% by weight (1.6 mol) with xylene was used as a raw material.
I got 8I.

Example 2 Fraction 7 consisting of 76.7% by weight of cyclopentadiene and saturated hydrocarbons obtained by steam cracking of naphtha
00J (contains 864 moles when dicyclopentadiene is calculated as cyclopentadiene). Styrene obtained from naphtha steam Clara Kinkukara, o, m,
C9 fraction 3 containing a total of 26.5% by weight (average molecular weight 118) of p-vinyltoluene, α, β-methylstyrene, and indesi, and mainly consisting of inert aromatic hydrocarbons.
001 (containing 0.67 mol of reactive component) was copolymerized in the same manner as in Example 1 to obtain a resin 630.9 having a softening point of 178°C.

Comparative Example 2 Using the same raw materials as in Example 2, copolymerization was carried out under the same conditions as in Comparative Example IA to obtain 665 g of a copolymer resin having a softening point of 158°C.

Example 3 A copolymer resin 647II having a softening point of 165°C was obtained in the same manner as in Example 2, except that the unreacted 09 aromatic fraction was removed and the subsequent polymerization temperature was 235°C.

Comparative Example 3 A copolymer resin 676I having a softening point of 167° C. was obtained in the same manner as in Comparative Example 2 except that the polymerization time was 5 hours.

The main manufacturing conditions for each pair and the properties of the obtained resin are summarized in Table 1.

Comparing Example 1 and Comparative Example 1, it is clear from the table that if the method of the present invention is followed, the softening point is 17% lower than that of the conventional method.
A copolymer resin with a high temperature can be obtained. Comparative Example IB is an example in which copolymerization was carried out by lowering the blending ratio of C9 aromatic hydrocarbons as one means for raising the softening point using a conventional method. It is true that even with the conventional method, it is possible to obtain a copolymer resin with a high softening point by lowering the blending ratio of C0-based aromatic hydrocarbons, but with this method, the composition ratio of C9-based aromatic hydrocarbons in the resin is approximately 273%. It will drop below. Example 2 and Comparative Example 2 are examples in which the C9 fraction obtained from steam cracking of naphtha was used as the raw material for C9 aromatic hydrocarbons, and the experiment was also carried out when the C9 aromatic hydrocarbons had a low blending ratio. Similar results to Example 1 were obtained.

Example 3 and Comparative Example 3 compare the manufacturing conditions for obtaining the same softening point using the method of the present invention and the conventional method, and show that the method of the present invention takes much less time than the conventional method. Furthermore, a high softening point copolymer resin can be obtained by processing at low temperatures.

Figure 1 shows the differential molecule 1 distribution of the intermediate resin immediately after removing the unreacted C9-based aromatic carbide ice, etc. in Example 1, and the resin of the final product that was subsequently polymerized. It is understood that the polymerization continues even after the uncured 15Cg-based aromatic hydrocarbons are removed.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing the differential molecular weight distribution of the intermediate resin immediately after removing unreinforced ECg-based aromatic hydrocarbons and the like in Example IK, and the resin of the final product that was further polymerized thereafter. Patent publication] person circle book petrochemical stock fee company fee]! :(Human masu burying person Ka embryo early・'1.' Bidopa

Claims (1)

[Claims] C_9 aromatic hydrocarbon consisting of 1 mole of cyclopentadiene and one or more selected from aromatic hydrocarbons having ethylenically unsaturated bonds and indesi 0.8 to 0.06
A high softening method characterized by thermally copolymerizing C_9-based aromatic hydrocarbons with moles in a temperature range of 220 to 320°C, removing unreacted C_9 aromatic hydrocarbons, and further thermally polymerizing in a temperature range of 150 to 300°C. A method for producing point cyclopentadiene petroleum resin.