CN108017759B

CN108017759B - Modified pentadiene hydrogenated petroleum resin and preparation method thereof

Info

Publication number: CN108017759B
Application number: CN201610966259.0A
Authority: CN
Inventors: 黄勇; 许惠明; 孙春水; 孙荣华; 王萍; 王世卿; 罗群
Original assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Petrochemical Co Ltd
Current assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Petrochemical Co Ltd
Priority date: 2016-10-28
Filing date: 2016-10-28
Publication date: 2021-06-01
Anticipated expiration: 2036-10-28
Also published as: CN108017759A

Abstract

The invention discloses a modified pentadiene hydrogenated petroleum resin and a preparation method thereof. The method comprises the steps of firstly, taking an imidazole compound as a modifier, and adding the modifier in a piperylene polymerization process to prepare piperylene modified petroleum resin; and then catalytically hydrogenating the piperylene modified petroleum resin to prepare the modified piperylene hydrogenated petroleum resin. The modified pentadiene hydrogenated petroleum resin obtained by the invention has high thermal stability, good compatibility with elastomers (such as SIS, SBS and the like) in hot melt adhesive and relatively light color.

Description

Modified pentadiene hydrogenated petroleum resin and preparation method thereof

Technical Field

The invention relates to a modified pentadiene hydrogenated petroleum resin and a preparation method thereof, belonging to the technical field of petrochemical industry.

Background

With the continuous development of various fields, the quality requirement of petroleum resin is higher and higher, wherein the development of the application of the adhesive and the sealant, in particular the application of the modifier of transparent pressure-sensitive adhesive tape, outdoor sealant, disposable sanitary products, medical adhesive tape, road marking paint and polyolefin, requires the petroleum resin with light color, no odor and good stability.

Because the carbon five resin has the defects of large brittleness, lack of polar groups on molecules, deep color and the like, in order to widen the application field of the resin, the prior art improves the performance of the petroleum resin by adding a modifier for copolymerization, for example, in Chinese patent application CN201410494202.6, the cyclopentadiene/dicyclopentadiene or styrene is added for copolymerization by taking pentadiene-rich fraction separated by ethylene cracking as a raw material, and the color and the molecular weight distribution of a resin product are improved; the Chinese patent application CN201310237557.2 takes acrylic acid as a grafting monomer to obtain modified C5 petroleum resin, and the product is mainly used as additives such as adhesives, printing ink, paint and the like; U.S. Pat. No. 4, 82757986A and EP1987030111 propose modifying copolymerized petroleum resins after modification by adding an aromatic compound which boils between 80 and 260 ℃ during polymerization to give a sufficient aromatic content. JP59236846 copolymerizes maleic anhydride and cyclopentadiene or piperylene to improve the flow characteristics and processability of the copolymer, and is particularly suitable for use as an electrical insulating resin casting.

As described above, the conventional art uses an aromatic compound, an olefin and an acid anhydride as a comonomer of piperylene, and only improves on a certain aspect, so that the range of use thereof is limited. Functional monomers of imidazole groups with special and active structures are not reported, a hotspot in the field of high polymer materials is the preparation and application of polymer microspheres, and the polymer microspheres from nano-scale to micron-scale are widely applied to many high and new technical fields of analytical chemistry, biomedicine, standard metering, solid phase carriers, high performance liquid chromatography and the like due to the special properties of large specific surface area, strong adsorbability, large condensation effect, strong surface reaction capability and the like.

Disclosure of Invention

In order to overcome the defects of the prior art, the invention aims to provide a modified pentadiene hydrogenated petroleum resin and a preparation method thereof. The invention adds imidazole compound to modify in the polymerization process of piperylene, and produces multifunctional hydrogenated petroleum resin with high thermal stability, good compatibility with elastomer (such as SIS and SBS) in hot melt adhesive and relatively light color through less harsh hydrogenation conditions.

The technical scheme of the invention is specifically introduced as follows.

The invention provides a preparation method of modified m-pentadiene hydrogenated petroleum resin, which comprises the following specific steps:

(1) adding piperylene, a catalyst, a modifier and an organic solvent into a reaction kettle, and carrying out catalytic polymerization reaction under normal pressure to obtain piperylene modified petroleum resin; wherein: the catalyst is Lewis acid, and the modifier is an imidazole compound;

(2) and (2) carrying out catalytic hydrogenation reaction on the piperylene modified petroleum resin obtained in the step (1) to obtain hydrogenated petroleum resin.

In the step (1), the organic solvent is selected from one or more of cyclopentane, cyclohexane, benzene, toluene and xylene.

In the step (1), the catalyst is boron trifluoride-diethyl ether or aluminum trichloride.

In the step (1), the modifier is propenyl imidazole or N-vinyl imidazole.

In the step (1), the mass ratio of piperylene to organic solvent is 1: 1-1: 5, the mass ratio of the modifier to the piperylene is 1: 2-1: 8, the mass ratio of the catalyst to the piperylene is 1: 40-1: 100, the reaction temperature is 40-100 ℃, and the reaction time is 180-360 min. Preferably, the mass ratio of piperylene to organic solvent is 1: 1-1: 2, the mass ratio of the modifier to the piperylene is 1: 4-1: 6, the mass ratio of the catalyst to the piperylene is 1: 60-1: 80, the reaction temperature is 60-80 ℃, and the reaction time is 240-300 min.

In the step (2), the catalyst is a skeletal nickel catalyst. Preferably, the nickel content in the skeletal nickel catalyst is 40-80 wt%, and the average pore diameter is 2.0-20.0 nm.

In the step (2), the mole ratio of the piperylene modified petroleum resin to the hydrogen is 1: 2-1: 5, the dosage of the catalyst is 0.5-3.0 wt% of the pentadiene modified petroleum resin, the reaction time is 120-300 min, the reaction pressure is 4.0-10.0 MPa, and the reaction temperature is 170-250 ℃. Preferably, the amount of the catalyst is 1.0-2.0 wt% of the piperylene modified petroleum resin, the reaction time is 180-240 min, the reaction pressure is 6.0-8.0 MPa, and the reaction temperature is 200-220 ℃.

The invention also provides the modified m-pentadiene hydrogenated petroleum resin prepared by the preparation method.

The modifier is a functional monomer containing active imidazole groups, has a special structure, a vinyl group in a molecular structure is directly connected with a nitrogen atom of an imidazole ring, and the vinyl group and a carbonyl group are in unconjugated structures, which are different from an acrylamide structure. The modified pentadiene hydrogenated petroleum is a linear polymer with lower molecular weight, and the functional group is introduced into the pentadiene resin, so that the thermal stability of the modified pentadiene hydrogenated petroleum can be greatly improved, the mixing and dispersion with other resins are promoted, the modified pentadiene hydrogenated petroleum also has good compatibility with elastomers (such as SIS, SBS and the like) in a hot melt adhesive, and meanwhile, the modified resin has relatively light color, and the tackifier resin with light color can be obtained only under the less harsh hydrogenation condition.

Detailed Description

The invention is further described below by means of specific embodiments.

Examples 1-10 preparation of hydrogenated Petroleum resins according to the following procedure: the reaction raw material is material rich in piperylene, the main composition is shown in table 1, the process conditions of each step are shown in table 2 (step 1), table 3 (step 1) and table 4 (step 2), after the reaction is finished, each index (softening point, molecular weight distribution, bromine value and the like) of the resin sample is weighed and analyzed, the result is shown in table 5, and the miscibility of the resin sample and other polymers is shown in table 5See table 6. Determining resin product molecular weight distribution index (M) by gel chromatography_w/M_n) The softening point was analyzed by the ring and sphere method GB/2294, and the bromine number was analyzed by the iodometry method (SWB 2301-62).

1) Adding a pentadiene raw material, an organic solvent, a catalyst and a modifier into a reaction kettle, carrying out catalytic polymerization reaction under normal pressure, and neutralizing and washing to remove the catalyst to generate the pentadiene modified petroleum resin.

2) Carrying out hydrogenation reaction on the petroleum resin obtained in the step 1) under the action of a skeletal nickel catalyst to obtain high-quality hydrogenated petroleum resin.

3) Recovering the solvent from the material obtained in the step 2) to obtain the high-quality hydrogenated petroleum resin.

Table 1.

Components	Content (wt.%)
		Piperylene of piperylene	67
Cyclopentene	19
		Cyclopentane	6.0
DCPD	2.0
		Others	6.0

TABLE 2

TABLE 3

TABLE 4

	Catalyst dosage/wt%	Reaction temperature/. degree.C	Reaction pressure/Mpa	Reaction time/min
					Example 1	0.5	250	10.0	120
Example 2	1.0	220	8.0	180
					Example 3	1.3	205	6.0	220
Example 4	1.1	210	7.0	210
					Example 5	1.5	206	6.2	225
Example 6	1.8	210	7.2	200
					Example 7	1.6	205	6.5	230
Example 8	2.0	220	7.5	190
					Example 9	2.5	200	6.8	240
Example 10	3.0	170	4.0	300

TABLE 5

TABLE 6

Claims

1. A preparation method of modified m-pentadiene hydrogenated petroleum resin is characterized by comprising the following specific steps:

(1) adding piperylene, a catalyst, a modifier and an organic solvent into a reaction kettle, and carrying out catalytic polymerization reaction under normal pressure to obtain piperylene modified petroleum resin; wherein: the catalyst is Lewis acid, and the modifier is propenyl imidazole or N-vinyl imidazole;

2. The method according to claim 1, wherein in the step (1), the organic solvent is selected from any one or more of cyclopentane, cyclohexane, benzene, toluene, and xylene.

3. The method according to claim 1, wherein in the step (1), the catalyst is boron trifluoride-diethyl ether or aluminum trichloride.

4. The method according to claim 1, wherein in the step (1), the mass ratio of piperylene to the organic solvent is 1: 1-1: 5, the mass ratio of the modifier to the piperylene is 1: 2-1: 8, the mass ratio of the catalyst to the piperylene is 1: 40-1: 100, the reaction temperature is 40-100 ℃, and the reaction time is 180-360 min.

5. The method according to claim 4, wherein the mass ratio of piperylene to organic solvent is 1: 1-1: 2, the mass ratio of the modifier to the piperylene is 1: 4-1: 6, the mass ratio of the catalyst to the piperylene is 1: 60-1: 80, the reaction temperature is 60-80 ℃, and the reaction time is 240-300 min.

6. The method according to claim 1, wherein in the step (2), the catalyst is a skeletal nickel catalyst.

7. The method of claim 6, wherein the skeletal nickel catalyst comprises 40 to 80 wt% nickel and has an average pore size of 2.0 to 20.0 nm.

8. The method according to claim 1, wherein in the step (2), the mole ratio of the piperylene modified petroleum resin to the hydrogen gas is 1: 2-1: 5, the dosage of the catalyst is 0.5-3.0 wt% of the pentadiene modified petroleum resin, the reaction time is 120-300 min, the reaction pressure is 4.0-10.0 MPa, and the reaction temperature is 170-250 ℃.

9. A modified piperylene hydrogenated petroleum resin obtained by the preparation method according to any one of claims 1 to 8.