CN111704684B

CN111704684B - Method for modifying C5/C9 copolymer resin by using peracetic acid

Info

Publication number: CN111704684B
Application number: CN202010692971.2A
Authority: CN
Inventors: 王斌; 孙向东
Original assignee: Henghe Materials and Science Technology Co Ltd
Current assignee: Henghe Materials and Science Technology Co Ltd
Priority date: 2020-07-17
Filing date: 2020-07-17
Publication date: 2023-03-21
Anticipated expiration: 2040-07-17
Also published as: CN111704684A

Abstract

The invention relates to a method for modifying C5/C9 copolymer resin by using peroxyacetic acid, which comprises the following steps: mixing C5 and C9 fractions to obtain a polymerization raw material, carrying out catalytic polymerization to obtain a polymerization solution, carrying out alkaline washing and water elution catalysis, and carrying out steam stripping to remove a solvent to obtain a molten resin solution; and mixing and modifying the molten resin liquid and peroxyacetic acid in a double-screw stirring extruder to obtain the modified C5/C9 copolymer resin. According to the invention, peracetic acid is added as an initiator to induce C5/C9 copolymerized petroleum resin to perform a ring-opening reaction, so that the unsaturation degree of the petroleum resin product is reduced, and the resin smell is reduced; meanwhile, the method has the advantages of low cost, simple process and good application prospect.

Description

Method for modifying C5/C9 copolymer resin by using peroxyacetic acid

Technical Field

The invention belongs to the field of petroleum resin, and particularly relates to a method for modifying C5/C9 copolymer resin by using peracetic acid.

Background

Petroleum resins are thermoplastic resins produced by polymerizing C5 fractions and C9 fractions among ethylene cracking byproducts, and can be generally classified into: aliphatic hydrocarbon resin (C5), aliphatic hydrocarbon-aromatic hydrocarbon resin (C5/C9), aromatic hydrocarbon resin (C9), and dicyclopentadiene resin (DCPD). Wherein, because the raw materials in the C5/C9 copolymer resin contain naphthalene, dicyclopentadiene, methylcyclopentadiene dimer and the like, more double bonds and aromatic hydrocarbon groups are still remained in the molecule after the copolymer resin is polymerized into the resin, so that the copolymer resin has the defects of larger smell, poorer thermal stability and the like, and the further application of the copolymer resin is limited.

Disclosure of Invention

The technical problem to be solved by the invention is to provide a method for modifying C5/C9 copolymerized resin by using peracetic acid (PAA), wherein the method induces the C5/C9 copolymerized petroleum resin to generate ring-opening reaction by adding PAA (poly (acrylic acid)) as an initiator, so that the unsaturation degree of the resin is reduced, and further the smell of the resin is reduced.

The invention provides a method for modifying C5/C9 copolymer resin by using peracetic acid, which comprises the following steps:

(1) Uniformly mixing the C5 and C9 fractions according to the mass ratio of 1 (0.1-9.0) to obtain a polymerization raw material; adding a solvent in a reactor with stirring in advance, then respectively and uniformly dropwise adding the polymerization raw materials and the catalyst, wherein the feeding time is 1.0-2.0 h, the reaction temperature is-10-30 ℃, and then carrying out heat preservation reaction at 20-50 ℃ for 0.5-2.0 h to obtain a polymerization solution;

(2) Adding excessive sodium hydroxide solution into the polymerization solution at 35-70 ℃ to remove a catalyst by alkali washing, washing the polymerization solution to be neutral by using clear water, and then removing unreacted raw materials and a solvent by steam stripping at 220-250 ℃ and under the pressure of 105-130 kPa to obtain a molten resin solution;

(3) And (3) stirring and mixing the molten resin liquid and peroxyacetic acid at the temperature of between 80 and 150 ℃ for 3 to 30 minutes in a double-screw stirring extruder to obtain the modified C5/C9 copolymer resin.

The solvent in the step (1) is one or more of cyclohexane, methylcyclohexane, toluene, xylene, petroleum ether, mineral oil and white oil, and the addition amount is 30-50 wt% of the total material mass.

The catalyst in the step (1) is Freidel-Crafts catalyst, and the addition amount of the catalyst is 0.2-2 wt% of the total mass of the materials.

The Freidel-Crafts catalyst is one of gaseous boron trifluoride, a boron trifluoride complex, anhydrous ferric trichloride and anhydrous aluminum trichloride.

The medium selected for stripping in the step (2) is one or more of methane, ethane and propane.

The addition amount of the peroxyacetic acid in the step (3) is 0.5 to 5.0wt% of the mass of the molten resin liquid.

The modified C5/C9 copolymer resin obtained in the step (3) has a softening point of 90-130 ℃, an odor score of less than or equal to 3.0 and a VOCs content of less than or equal to 1.5wt%.

Advantageous effects

(1) According to the invention, peracetic acid is added as an initiator to induce C5/C9 copolymerized petroleum resin to perform a ring-opening reaction, so that the unsaturation degree of the petroleum resin product is reduced, and the resin smell is reduced; meanwhile, the method has low cost, simple process and good application prospect;

(2) The invention preferably adopts methane as a stripping medium, improves the effect of removing resin solvent and oligomer, reduces resin VOCs, and further reduces resin odor.

Detailed Description

The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.

Cracking C5 fraction composition main compound composition

Components	Content (a) of	Components	Content (a) of
				1-butene + isobutene	0.49	2-methyl-2-butene	1.74
1, 3-butadiene	1.22	Trans-1, 3-pentadiene	20.02
				N-butane	0.03	Cyclopentadiene	10.78
Butene-2	0.19	Cyclopentene	14.92
				Cis-buten-2	0.23	Cyclopentane	3.39
2-methyl-butane	2.16	2, 3-dimethylbutane	0.76
				1, 2-butadiene	0.07	2-methylpentane	0.19
3-methyl-1-butene	0.85	2-methyl-1-pentene	0.27
				Isopentane	1.64	N-hexane	0.87
1, 4-pentadiene	2.71	Methylcyclopentane	0.79
				2-butyne	0.94	Benzene and its derivatives	0.76
1-pentene	6.13	Dicyclopentadiene	6.11
				2-methyl-butene-1	4.27	Heavy fraction	2.50
N-pentane	4.52	Unknown object	2.43
				Isoprene (I)	4.34
Trans-2-pentene	2.85

Ethylene byproduct C9 fraction main compound composition

Serial number	Name of Compound	Content (a) of	Serial number	Name of Compound	Content (a) of
						1	Cyclopentadiene	0.75	17	Diethyl-1, 3-xylene	1.54
2	1-methylcyclopentadiene	0.87	18	Bicyclo [2,2 ]]Oct-2-ene	4.62
						3	Spiro [2,4 ]]-hepta-4,6 diene	0.20	19	4-ethylene-1, 2-xylene	1.99
4	Ethylbenzene production	0.13	20	1-ethylene-2, 3-xylene	0.43
						5	Para-xylene	0.82	21	1,2,4, 5-tetramethylbenzene	1.00
6	Ortho-and meta-xylene	3.29	22	1-ethylene-2, 4-xylene	1.06
						7	Cyclopropyl benzene	7.28	23	2, 4-Dimethylstyrene	0.97
8	Propyl benzene	0.68	24	4-vinyl-1, 2-xylene	0.31
						9	1-methyl-2-toluene	4.56	25	2-BEne-1, 4-xylenes	0.20
10	Trimethylbenzene	2.68	26	1, 3-dimethyl-5-toluene	0.30
						11	Alpha-methylstyrene	2.71	27	2-methylindene	3.26
12	1-vinyl-3-toluene	13.15	28	1-methyl-1-hydroindene	2.31
						13	Dicyclopentadiene	11.08	29	Naphthalene	5.37
14	Indene	7.29	30	Dodecane	0.53
						15	Tetraethyl-1, 2-xylene	1.52	31	2-methylnaphthalene	0.44
16	1-methyl-2-propylbenzene	0.32

Petroleum resin odor test method:

with reference to the german automobile industry association standard VDA 270 (1992 EN) requirements for odor emission of automotive interior parts, the odor test method and evaluation rating of petroleum resin are specified as follows:

putting 1.0 +/-0.05 g of resin into a 250mL closed container, baking at the temperature of 80 +/-2 ℃ for 2h +/-2 min, cooling to room temperature, and performing odor evaluation on 3 testers respectively. The evaluation grade is divided into 1-6 grades, the minimum evaluation unit is 0.5, and the final test result is obtained by 3 scoring and averaging.

The specific criteria are as follows:

example 1

Uniformly mixing C5 and C9 fractions according to a mass ratio of 1. The resin liquid is washed by excessive 10 percent sodium hydroxide solution at 65 ℃ to remove a catalyst, then washed by clean water to be neutral, and stripped by taking methane as a medium at 230 ℃ and 115kPa to remove unreacted raw materials and solvent, so as to obtain the molten resin liquid with the softening point of 103.2 ℃, the color number of 4.7#, the odor score of 5.5 and the VOCs content of 6.85 percent.

The molten resin solution was mixed with 0.8wt% PAA at 95 ℃ for 5 minutes in a twin-screw stirring extruder to obtain a modified C5/C9 copolymer resin having a softening point of 107.2 ℃, a color number of 4.9#, an odor score of 2.5, and a VOCs content of 3.50%.

Examples 2 to 6

Examples 2 to 6 are resin properties comparisons obtained under different modification conditions of the molten resin liquids having a softening point of 103.2 ℃, a color number of 4.7#, an odor score of 5.5, and a VOCs content of 6.85% obtained by the method of example 1.

From the above examples, it is understood that when the amount of PAA used is increased and the reaction time is prolonged, the softening point and the weight average molecular weight Mw of the modified copolymer resin can be significantly increased, but the color number of the resin is easily deteriorated. An increase in the reaction temperature is advantageous for reducing the odor of the resin and the content of VOCs, but at the same time leads to a deepening of the color number of the resin and an increase in the weight-average molecular weight Mw.

The odor of the C5/C9 copolymer resin liquid before modification is relatively heavy, and the modified resin still has no pungent odor.

Example 7

Uniformly mixing C5 and C9 fractions according to the mass ratio of 1: 0.1 to obtain a polymerization raw material, firstly putting dimethylbenzene accounting for 40% of the total mass of the raw material as a solvent in a reactor with a stirrer, then uniformly dropwise adding the polymerization raw material and a boron trifluoride diethyl etherate catalyst accounting for 1.0% of the total mass of the raw material respectively, wherein the feeding time is 1.0h, the reaction temperature is 0 ℃ during dropwise adding, and then carrying out heat preservation reaction at 25 ℃ for 1.0h to obtain a polymerization solution. The resin liquid is washed by excessive 10 percent sodium hydroxide solution at 65 ℃ to remove a catalyst, then washed by clean water to be neutral, and stripped by taking methane as a medium at 230 ℃ and 115kPa to remove unreacted raw materials and solvent, so as to obtain the molten resin liquid with the softening point of 98.7 ℃, the color number of 3.3#, the odor score of 3.7 and the VOCs content of 3.56%.

Mixing the molten resin solution with 1.5% PAA at 125 deg.C for 5min in a twin-screw stirring extruder to obtain modified C5/C9 copolymer resin with softening point of 102.2 deg.C, color number of 3.5#, odor score of 1.5, and VOCs content of 1.89%.

Example 8

Uniformly mixing C5 and C9 fractions according to the mass ratio of 1: 1 to obtain a polymerization raw material, firstly putting dimethylbenzene accounting for 40% of the total mass of the raw material as a solvent in a reactor with a stirrer, then respectively and uniformly dropwise adding the polymerization raw material and a boron trifluoride diethyl etherate catalyst accounting for 0.8% of the total mass of the raw material for 1.0h, wherein the reaction temperature is 0 ℃ during dropwise adding, and then carrying out heat preservation reaction at 35 ℃ for 2.0h to obtain a polymerization solution. The resin liquid is washed by excessive 10 percent sodium hydroxide solution at 65 ℃ to remove a catalyst, then washed by clean water to be neutral, and stripped by taking ethane as a medium at 250 ℃ and under the pressure of 105kPa to remove unreacted raw materials and solvent, so as to obtain the molten resin liquid with the softening point of 101.0 ℃, the color number of 4.0#, the odor score of 4.5 and the VOCs content of 2.26%.

In a twin-screw stirring extruder, the above molten resin solution was mixed with 1.0% PAA at 120 ℃ for 10min to obtain a modified C5/C9 copolymer resin having a softening point of 104.4 ℃, a color number of 4.5#, a smell score of 2.0, and a VOCs content of 1.50%.

Claims

1. A method of modifying a C5/C9 copolymer resin with peroxyacetic acid, comprising:

(2) Adding excessive sodium hydroxide solution into the polymerization solution at 35-70 ℃ to carry out alkali washing to remove the catalyst, washing the polymerization solution with clear water to be neutral, and then stripping at 220-250 ℃ and 105-130 kPa to remove unreacted raw materials and solvent to obtain molten resin solution;

(3) In a double-screw stirring extruder, stirring and mixing the molten resin liquid and peroxyacetic acid at the temperature of between 80 and 150 ℃ for 3 to 30min to obtain modified C5/C9 copolymer resin; wherein the addition amount of the peroxyacetic acid is 0.5 to 5.0 weight percent of the mass of the molten resin liquid; the softening point of the obtained modified C5/C9 copolymer resin is 90-130 ℃, the odor score is less than or equal to 3.0, and the content of VOCs is less than or equal to 1.5wt%.

2. The method of claim 1, wherein: the solvent in the step (1) is one or more of cyclohexane, methylcyclohexane, toluene, xylene, petroleum ether, mineral oil and white oil, and the addition amount of the solvent is 30-50 wt% of the total mass of the materials.

3. The method of claim 1, wherein: the catalyst in the step (1) is Freidel-Crafts catalyst, and the addition amount of the catalyst is 0.2-2 wt% of the total mass of the materials.

4. The method of claim 3, wherein: the Freidel-Crafts catalyst is one of gaseous boron trifluoride, a boron trifluoride complex, anhydrous ferric trichloride and anhydrous aluminum trichloride.

5. The method of claim 1, wherein: the medium selected for stripping in the step (2) is one or more of methane, ethane and propane.