阅读说明：本技术 一种柔性氢化c9石油树脂的制备方法 (Preparation method of flexible hydrogenated C9 petroleum resin ) 是由 李爱元 孙向东 王斌 彭振博 张慧波 李芳� 李丹莹 于 2020-12-02 设计创作，主要内容包括：本发明属于石油树脂加工技术领域,具体涉及一种柔性氢化C9石油树脂的制备方法。本发明柔性氢化C9石油树脂的制备方法,依次包括马来酸双长链醇酯的制备,柔性C9石油树脂的制备,柔性氢化C9石油树脂的制备。本发明通过马来酸酐的酸酐基团与长链醇合成柔性单体,将柔性单体的双键和C9石油树脂的不饱和双键进行自由基共聚,生成柔性石油树脂,对柔性石油树脂加氢改性,合成柔性氢化石油树脂,该方法制备的C9石油树脂颜色浅,热稳定性良好,且柔性可调控,具有良好的工业应用前景。(The invention belongs to the technical field of petroleum resin processing, and particularly relates to a preparation method of flexible hydrogenated C9 petroleum resin. The preparation method of the flexible hydrogenated C9 petroleum resin sequentially comprises the preparation of the maleic acid double-long-chain alcohol ester, the preparation of the flexible C9 petroleum resin and the preparation of the flexible hydrogenated C9 petroleum resin. According to the invention, the acid anhydride group of maleic anhydride and long-chain alcohol are used for synthesizing the flexible monomer, the double bond of the flexible monomer and the unsaturated double bond of the C9 petroleum resin are subjected to free radical copolymerization to generate the flexible petroleum resin, and the flexible petroleum resin is subjected to hydrogenation modification to synthesize the flexible hydrogenated petroleum resin.)

1. The preparation method of the flexible hydrogenated C9 petroleum resin is characterized by sequentially comprising the preparation of the maleic acid double-long-chain alcohol ester, the preparation of the flexible C9 petroleum resin and the preparation of the flexible hydrogenated C9 petroleum resin.

2. The method according to claim 1, wherein the preparation of the bis-long chain alcohol maleate specifically comprises: adding maleic anhydride, long-chain alcohol, toluenesulfonic acid and water carrying agent into a four-mouth bottle with a stirrer, heating to 100 ℃ and 140 ℃ for esterification reaction, and after the reaction is finished, carrying out reduced pressure distillation, alkaline washing, water washing and vacuum drying on the product to obtain milky waxy maleic acid di-long-chain alcohol ester.

3. The method according to claim 2, wherein the long-chain alcohol is a normal alcohol having no branch on the carbon chain, and the number of carbon atoms on the carbon chain is 5 to 25.

4. The preparation method according to claim 2, wherein the mass percentages of the maleic anhydride, the long-chain alcohol, the toluenesulfonic acid and the water carrying agent are 18-40%, 58-80%, 0.5-2% and 1-1.5% in sequence.

5. The method according to claim 2 or 4, wherein the water carrying agent is at least one of petroleum ether, benzene, toluene, cyclohexane, chloroform and carbon tetrachloride.

6. The preparation method according to claim 1, wherein the flexible C9 petroleum resin is prepared by: adding C9 petroleum resin into a four-mouth bottle with a stirrer, heating to melt, adding maleic acid double-long-chain alcohol ester, adding a free radical polymerization initiator in batches at the temperature of 150-250 ℃, heating to the temperature of 260-300 ℃ after the initiator is added, and carrying out grafting reaction to obtain the flexible petroleum resin after the reaction is finished.

7. The method according to claim 6, wherein the amount of the di-long chain alcohol maleate is 5-30% of the total mass of the C9 petroleum resin, and the amount of the radical polymerization initiator is 0.5-2.5% of the total mass of the C9 petroleum resin.

8. The production method according to claim 6 or 7, wherein the radical polymerization initiator is at least one of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate initiator, benzoyl peroxide t-butyl peroxide, methyl ethyl ketone peroxide.

9. The method according to claim 1, wherein the flexible hydrogenated petroleum resin is prepared by: dissolving the flexible petroleum resin with saturated alkane or saturated cyclane, and then carrying out two-stage hydrogenation reaction to prepare the flexible hydrogenated petroleum resin.

10. The preparation method according to claim 9, wherein the two-stage hydrogenation reaction is specifically: the first stage hydrogenation adopts a nickel catalyst, the temperature is 150-350 ℃, the pressure is 3-8MPa, and the liquid space velocity is 0.1-1.0h^-1Completing unsaturated double bond hydrogenation and desulfurization; the second stage hydrogenation adopts palladium catalyst with the temperature of 150 ℃ and 350 ℃, the pressure of 6-16MPa and the liquid space velocity of 0.1-1.0h^-1And finishing the hydrogenation of aromatic hydrocarbon.

Technical Field

The invention belongs to the technical field of petroleum resin processing, and particularly relates to a preparation method of flexible hydrogenated C9 petroleum resin.

Background

The C9 resin is insoluble in water and soluble in organic solvents, has excellent performances of acid resistance, alkali resistance, ageing resistance and the like, has wide sources and low price, has wide application fields, and can be applied to the industries of road marking paint, adhesives, rubber, tires, plastics, papermaking, printing ink and the like. However, the common petroleum resin stone has the defects of dark color, low thermal stability, large brittleness and the like due to the existence of more unsaturated double bonds, aromatic hydrocarbons, halide impurities in the polymerization process and the like, so that the industrial application is limited.

In order to solve the problems, hydrogenation modification is mostly adopted at present to modify the petroleum resin, the hydrogenation modification can saturate unsaturated double bonds and aromatic hydrocarbons in the petroleum resin and remove residual halogen elements, the modified resin is colorless and has no special smell, and the performances such as weather resistance, adhesion, stability and the like of the modified resin can be improved, but the hydrogenation modification still does not overcome the problem of large brittleness of the petroleum resin, but the resin becomes nonpolar after hydrogenation to influence the application of the resin, for example, the hydrogenation modified C9 petroleum resin such as Chinese patent CN2019103862953, CN2017100737577, CN2018114110240 and the like. Therefore, it is imperative to find a new modification method which can ensure light color and good thermal stability of the C9 petroleum resin and overcome the defect of large brittleness.

Disclosure of Invention

The invention aims to solve the problems in the prior art, and provides a preparation method of flexible hydrogenated C9 petroleum resin, which solves the problems of dark color and poor thermal stability of C9 petroleum resin and large brittleness, and can realize the regulation and control of the flexibility of the petroleum resin through reaction process control.

The above object of the present invention can be achieved by the following technical solutions: a preparation method of a flexible hydrogenated C9 petroleum resin sequentially comprises the preparation of a maleic acid double-long-chain alcohol ester, the preparation of a flexible C9 petroleum resin and the preparation of a flexible hydrogenated C9 petroleum resin.

Preferably, the preparation of the maleic acid di-long-chain alcohol ester specifically comprises the following steps: adding maleic anhydride, long-chain alcohol, toluenesulfonic acid and water carrying agent into a four-mouth bottle with a stirrer, heating to 100 ℃ and 140 ℃ for esterification reaction, and after the reaction is finished, carrying out reduced pressure distillation, alkaline washing, water washing and vacuum drying on the product to obtain milky waxy maleic acid di-long-chain alcohol ester.

More preferably, the long-chain alcohol is a normal alcohol having no branch on the carbon chain, and the number of carbon atoms on the carbon chain is 5 to 25. For the purposes of this application, too small a molecular weight does not contribute to the modification, but too large a molecular weight also affects the modification.

More preferably, the mass percentages of the maleic anhydride, the long-chain alcohol, the toluenesulfonic acid and the water carrying agent are 18-40%, 58-80%, 0.5-2% and 1-1.5% in sequence.

Still more preferably, the water carrying agent is at least one of petroleum ether, benzene, toluene, cyclohexane, chloroform and carbon tetrachloride.

Preferably, the preparation of the flexible C9 petroleum resin is specifically as follows: adding C9 petroleum resin into a four-mouth bottle with a stirrer, heating to melt, adding maleic acid double-long-chain alcohol ester, adding a radical polymerization initiator in batches at 250 ℃ in equal amount, heating to 300 ℃ after the initiator is added, and carrying out grafting reaction to obtain the flexible petroleum resin. According to the invention, the initiator is added in batches, so that the reaction process can be carried out stably and safely, and in the actual operation process, the reaction liquid is splashed when the initiator is added at one time, so that the reaction process is unstable, more byproducts are generated, and the yield and the performance of the product are reduced.

More preferably, the adding amount of the maleic acid double-long-chain alcohol ester is 5-30% of the total mass of the C9 petroleum resin, and the adding amount of the free radical polymerization initiator is 0.5-2.5% of the total mass of the C9 petroleum resin.

More preferably, the radical polymerization initiator is at least one of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, benzoyl peroxide tert-butyl peroxide, and methyl ethyl ketone peroxide.

Preferably, the preparation of the flexible hydrogenated petroleum resin is specifically as follows: dissolving flexible petroleum resin with saturated alkane or saturated cycloalkane at concentration of 1-20%, and performing two-stage hydrogenation with nickel catalyst with high sulfur poisoning resistance at 150-350 deg.C under 3-8MPa and liquid space velocity of 0.1-1.0h^-1Completing unsaturated double bond hydrogenation and desulfurization; the second stage hydrogenation adopts palladium catalyst with the temperature of 150 ℃ and 350 ℃, the pressure of 6-16MPa and the liquid space velocity of 0.1-1.0h^-1And finishing the hydrogenation of the aromatic hydrocarbon to finally obtain the flexible hydrogenated petroleum resin. The invention adopts two-stage hydrogenation to avoid that the arene in the flexible hydrogenated petroleum resin can not be hydrogenated only by adopting the first-stage hydrogenation on one hand, and avoids that the palladium catalyst is poisoned only by adopting the second-stage hydrogenation for too long reaction time.

The invention has the beneficial effects that:

according to the invention, the acid anhydride group of maleic anhydride and long-chain alcohol are used for synthesizing the flexible monomer, the double bond of the flexible monomer and the unsaturated double bond of the C9 petroleum resin are subjected to free radical copolymerization to generate the flexible petroleum resin, and the flexible petroleum resin is subjected to hydrogenation modification to synthesize the flexible hydrogenated petroleum resin.

Detailed Description

The following are specific examples of the present invention and illustrate the technical solutions of the present invention for further description, but the present invention is not limited to these examples. The raw materials used in the examples of the present invention are those commonly used in the art, and the methods used in the examples are those conventional in the art, unless otherwise specified.

Example 1

Weighing the following components in percentage by mass: 28 percent of maleic anhydride, 69 percent of n-octadecyl alcohol, 1.5 percent of toluenesulfonic acid and 1.5 percent of petroleum ether are sequentially added into a four-mouth bottle with a stirring device, a reflux condenser pipe and a water separator are arranged on the four-mouth bottle, then an electrothermal insulating sleeve is used for heating to 120 ℃ for esterification reaction, water generated by the reaction and a water carrying agent form an azeotrope to be evaporated out, the water is separated by the water separator, when the water yield removed by a system is equal to the theoretical water yield or the water yield is not increased any more, the esterification reaction is finished, and a product is subjected to reduced pressure distillation, alkali washing, water washing and vacuum drying to obtain milky waxy maleic acid di-n-octadecyl ester;

placing 100g of C9 petroleum resin into a four-mouth bottle with a stirring device, heating the bottle in an oil bath to a molten state, adding 10g of the prepared maleic acid di-n-octadecyl ester, then adding 1.5g of azobisisobutyronitrile in batches at 200 ℃, after the addition of the azobisisobutyronitrile is finished, heating the mixture to 280 ℃ for grafting reaction, and obtaining flexible petroleum resin after the reaction is finished;

dissolving the obtained flexible petroleum resin with saturated heptane to obtain solution with concentration of 15%, and placing in fixed bed reactor (stainless steel tubular reactor with all sizes) The hydrogenation reaction is carried out in the middle, two-stage hydrogenation is adopted, two stainless steel tube type reactors are completely the same, and NiMoS/gamma-Al for the first-stage hydrogenation₂O₃The catalyst has the temperature of 250 ℃, the pressure of 5MPa and the liquid space velocity of 0.6h^-1Completing unsaturated double bond hydrogenation and desulfurization; Pd/MgAl for second-stage hydrogenation₂O₄-Al₂O₃The catalyst has the temperature of 260 ℃, the pressure of 10MPa and the liquid space velocity of 0.6h^-1And finishing the hydrogenation of the aromatic hydrocarbon to obtain the flexible hydrogenated petroleum resin.

Example 2

Weighing the following components in percentage by mass: 18 percent of maleic anhydride, 80 percent of n-heptanol, 0.5 percent of toluenesulfonic acid and 1.5 percent of toluene are sequentially added into a four-mouth bottle with a stirring device, a reflux condenser pipe and a water separator are arranged on the four-mouth bottle, then an electric heating insulation sleeve is used for heating to 100 ℃ for esterification reaction, water generated by the reaction and a water carrying agent form an azeotrope to be evaporated, the water is separated by the water separator, when the water amount removed by a system is equal to the theoretical water yield or the water yield is not increased any more, the esterification reaction is finished, and a product is subjected to reduced pressure distillation, alkali washing, water washing and vacuum drying to obtain milky waxy n-heptanoyl maleate;

placing 100g of C9 petroleum resin into a four-mouth bottle with a stirring device, heating the bottle in an oil bath to a molten state, adding 5g of the prepared n-heptanol maleate, adding 0.5g of benzoyl peroxide in batches at 150 ℃, heating the mixture to 260 ℃ after the benzoyl peroxide is added, and carrying out grafting reaction to obtain flexible petroleum resin after the reaction is finished;

dissolving the obtained flexible petroleum resin with saturated C12 alkane to obtain a solution with a concentration of 10%, and placing the solution in a fixed bed reactor (the sizes of stainless steel tubular reactors are all equal) ) The hydrogenation reaction is carried out in the middle, two-stage hydrogenation is adopted, two stainless steel tube type reactors are completely the same, and NiMoS/gamma-Al for the first-stage hydrogenation₂O₃Catalyst with temperature of 150 ℃, pressure of 3MPa and liquid space velocity of 0.1h^-1Completing unsaturated double bond hydrogenation and desulfurization; Pd/MgAl for second-stage hydrogenation₂O₄-Al₂O₃Catalyst with temperature of 350 ℃, pressure of 6MPa and liquid space velocity of 0.1h^-1And finishing the hydrogenation of the aromatic hydrocarbon to obtain the flexible hydrogenated petroleum resin.

Example 3

Weighing the following components in percentage by mass: 28 percent of maleic anhydride, 69 percent of n-pentacosanol, 1.5 percent of toluenesulfonic acid and 1.5 percent of cyclohexane are sequentially added into a four-mouth bottle with a stirring device, a reflux condenser pipe and a water separator are arranged on the four-mouth bottle, then an electric heating insulation sleeve is used for heating to 120 ℃ to carry out esterification reaction, water generated by the reaction and a water carrying agent form an azeotrope to be evaporated, water is separated by the water separator, when the water amount removed from a system is equal to the theoretical water yield or the water yield is not increased any more, the esterification reaction is finished, and a product is subjected to reduced pressure distillation, alkaline washing, water washing and vacuum drying to obtain milky waxy maleic acid di-n-pentacosanol ester;

placing 100g of C9 petroleum resin into a four-mouth bottle with a stirring device, heating the bottle in an oil bath to a molten state, adding 15g of the prepared maleic acid di-n-pentacosanol ester, adding dimethyl azodiisobutyrate in batches at 180 ℃, heating the solution to 270 ℃ after the dimethyl azodiisobutyrate is added, and carrying out grafting reaction to obtain flexible petroleum resin after the reaction is finished;

dissolving the obtained flexible petroleum resin with cyclohexane at concentration of 15%, and placing in a fixed bed reactor (stainless steel tubular reactor with all sizes)) The hydrogenation reaction is carried out in the middle, two-stage hydrogenation is adopted, two stainless steel tube type reactors are completely the same, and NiMoS/gamma-Al for the first-stage hydrogenation₂O₃Catalyst with temperature of 180 ℃, pressure of 4MPa and liquid space velocity of 0.4h^-1Completing unsaturated double bond hydrogenation and desulfurization; Pd/MgAl for second-stage hydrogenation₂O₄-Al₂O₃The catalyst has the temperature of 160 ℃, the pressure of 8MPa and the liquid space velocity of 0.4h^-1And finishing the hydrogenation of the aromatic hydrocarbon to obtain the flexible hydrogenated petroleum resin.

Example 4

Weighing the following components in percentage by mass: 35 percent of maleic anhydride, 63 percent of n-dodecanol, 0.8 percent of toluenesulfonic acid and 1.2 percent of carbon tetrachloride are sequentially added into a four-mouth bottle with a stirring device, a reflux condenser pipe and a water separator are arranged on the four-mouth bottle, then an electric heating insulation sleeve is used for heating to 130 ℃ for esterification reaction, water generated by the reaction and a water carrying agent form an azeotrope to be evaporated, the water is separated by the water separator, when the water yield removed by a system is equal to the theoretical water yield or the water yield is not increased any more, the esterification reaction is finished, and a product is subjected to reduced pressure distillation, alkali washing, water washing and vacuum drying to obtain milky waxy di-n-dodecanol maleate;

placing 100g of C9 petroleum resin into a four-mouth bottle with a stirring device, heating the bottle in an oil bath to a molten state, adding 20g of the prepared di-n-dodecyl maleate, then adding 2g of benzoyl peroxide tert-butyl ester for 3 times at 230 ℃, after finishing adding the benzoyl peroxide tert-butyl ester, heating the solution to 290 ℃ for grafting reaction, and obtaining flexible petroleum resin after the reaction is finished;

dissolving the obtained flexible petroleum resin saturated cyclopentane with concentration of 18%, and placing in a fixed bed reactor (the sizes of stainless steel tubular reactors are all equal)) The hydrogenation reaction is carried out in the middle, two-stage hydrogenation is adopted, two stainless steel tube type reactors are completely the same, and NiMoS/gamma-Al for the first-stage hydrogenation₂O₃Catalyst with temperature of 300 ℃, pressure of 7MPa and liquid space velocity of 0.8h^-1Completing unsaturated double bond hydrogenation and desulfurization; Pd/MgAl for second-stage hydrogenation₂O₄-Al₂O₃Catalyst with temperature of 300 ℃, pressure of 15MPa and liquid space velocity of 0.8h^-1And finishing the hydrogenation of the aromatic hydrocarbon to obtain the flexible hydrogenated petroleum resin.

Example 5

Weighing the following components in percentage by mass: 40% of maleic anhydride, 58% of n-tetradecanol, 1% of toluenesulfonic acid and 1% of benzene are sequentially added into a four-mouth bottle with a stirring device, a reflux condenser pipe and a water separator are arranged on the four-mouth bottle, then an electrothermal insulating sleeve is used for heating to 140 ℃ for esterification reaction, water generated by the reaction and a water carrying agent form an azeotrope to be evaporated, water is separated by the water separator, when the water amount removed from a system is equal to the theoretical water yield or the water yield is not increased any more, the esterification reaction is finished, and a product is subjected to reduced pressure distillation, alkali washing, water washing and vacuum drying to obtain milky waxy di-n-tetradecyl maleate;

placing 100g of C9 petroleum resin into a four-mouth bottle with a stirring device, heating the bottle in oil bath to a molten state, adding 30g of the prepared maleic acid di-n-tetradecyl ester, then adding 2.5g of methyl ethyl ketone peroxide 3 times at 250 ℃, after the methyl ethyl ketone peroxide is added, heating the mixture to 300 ℃ for grafting reaction, and obtaining flexible petroleum resin after the reaction is finished;

dissolving the obtained flexible petroleum resin with saturated C18 alkane to obtain a solution with a concentration of 20%, and reacting in a fixed bedReactor (stainless steel tubular reactor all size) ) The hydrogenation reaction is carried out in the middle, two-stage hydrogenation is adopted, two stainless steel tube type reactors are completely the same, and NiMoS/gamma-Al for the first-stage hydrogenation₂O₃Catalyst with temperature of 350 ℃, pressure of 8MPa and liquid space velocity of 1.0h^-1Completing unsaturated double bond hydrogenation and desulfurization; Pd/MgAl for second-stage hydrogenation₂O₄-Al₂O₃Catalyst with temperature of 150 ℃, pressure of 16MPa and liquid space velocity of 1.0h^-1And finishing the hydrogenation of the aromatic hydrocarbon to obtain the flexible hydrogenated petroleum resin.

Comparative example 1

C9 petroleum resin body.

Comparative example 2

The only difference from example 1 is that the C9 petroleum resin was directly subjected to a two-stage hydrogenation reaction to obtain a hydrogenated C9 petroleum resin.

Comparative example 3

The difference from example 1 is only that azobisisobutyronitrile, a radical polymerization initiator, was added at one time during the preparation of the flexible petroleum resin.

Comparative example 4

The only difference from example 1 is that only the first stage hydrogenation reaction was used.

Comparative example 5

The only difference from example 1 is that only the second stage hydrogenation reaction was used.

Comparative example 6

A polypropylene body.

The detection method of each technical index of the invention comprises the following steps:

(1) determination of softening point: the determination is carried out according to the method of the asphalt softening point determination method, namely the global method (national standard GB/T4507-1999).

(2) Measurement of color intensity: the color is measured according to the method of measuring the color of the epoxy resin and the method of the Nardy colorimetric method (national standard GB/T222295-2008).

(3) The notched impact strength is tested according to GB/T1043-2008, the flexibility or brittleness of the flexible hydrogenated C9 petroleum resin is mainly measured by blending the flexible hydrogenated petroleum resin with other substances and then testing the notched impact strength of the blended material, therefore, the flexible hydrogenated petroleum resin accounting for 1 wt% of the total mass of the materials and 99 wt% of polypropylene are blended for 0.5h at 120 ℃, then the notched impact strength of the blended material is tested, and the flexibility or brittleness of the resin is evaluated through the numerical change of the impact strength.

The results of the property test of the flexible hydrogenated petroleum resins of examples 1 to 5 and comparative examples 1 to 6 are shown in Table 1:

table 1: results of Performance test of Flexible hydrogenated Petroleum resins in examples 1 to 5 and comparative examples 1 to 6

As can be seen from the test results in Table 1, the flexible hydrogenated petroleum resin prepared by the technical scheme of the invention has light color, small color change at high temperature and good high-temperature stability; the blending of the untreated C9 petroleum resin and the polypropylene not only does not improve the notch impact strength of the polypropylene, but also deteriorates the notch impact strength, but the blending of the modified flexible hydrogenated C9 petroleum resin and the polypropylene obviously improves the notch impact strength of the polypropylene, which indicates that the flexible hydrogenated petroleum resin has good flexibility or less brittleness. Therefore, the invention solves the problems of dark color, poor thermal stability and large brittleness by modifying the C9 petroleum resin, and has good industrial application value.

The technical scope of the invention claimed by the embodiments herein is not exhaustive and new solutions formed by equivalent replacement of single or multiple technical features in the embodiments are also within the scope of the invention, and all parameters involved in the solutions of the invention do not have mutually exclusive combinations if not specifically stated.

While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.