CN115975132A - Modified C9 hydrogenated petroleum resin, its preparation method and application - Google Patents

Abstract

The invention provides a modified C9 hydrogenated petroleum resin, a preparation method and application thereof. The preparation method of the modified C9 hydrogenated petroleum resin comprises the following steps: in the presence of an initiator, a polar grafting activator and a solvent, carrying out grafting reaction on the C9 hydrogenated petroleum resin and an acidifier to obtain a grafting product system, wherein the acidifier is unsaturated anhydride and/or unsaturated acid, and the polar grafting activator is selected from cinnamate activators and styrene activators; extracting the grafted product system with a strongly polar solvent to obtain an extracted product, wherein the solubility parameter of the strongly polar solvent is greater than 3.0 (cal/cm) ³ ) ^1/2 (ii) a And removing the solvent in the extraction product to obtain the modified C9 hydrogenated petroleum resin. The modified C9 hydrogenated petroleum resin prepared by the invention is used for improving the compatibility of the C9 hydrogenated petroleum resin and polar polymers such as EVA, PU and the like, can be used in the field of hot-melt pressure-sensitive adhesives, and improves the compatibility of the pressure-sensitive adhesives and polar materials, thereby improving the adhesive force.

Description

Modified C9 hydrogenated petroleum resin, its preparation method and application

technical field

The invention relates to the field of preparation of modified C9 hydrogenated petroleum resin, in particular to a modified C9 hydrogenated petroleum resin, its preparation method and application.

Background technique

Petroleum resin is a kind of raw material produced by pretreatment, polymerization _, distillation _, etc. thermoplastic resin. According to different raw materials, it is divided into aliphatic resin (C ₅ ), alicyclic resin (DCPD), aromatic resin (C ₉ ), aliphatic/aromatic copolymer resin (C ₅ /C ₉ ), C ₅ hydrogenated petroleum Resins and C ₉ Hydrogenated Petroleum Resins. Petroleum resin is cheap, low melting point, good water resistance and widely used in hot melt adhesive, pressure sensitive adhesive, rubber, paint, printing ink and other fields, but petroleum resin contains a large number of unsaturated bonds and does not contain polar groups, heat The petroleum resin produced by the polymerization process has dark color, poor thermal stability, strong odor, and poor compatibility with polar materials. Catalytic hydrogenation modification of double bonds and aromatic rings in C ₅ and C ₉ petroleum resins can also remove the residual halides in the resin during the polymerization process, improve the light and heat stability of the product, and obtain light color and thermal stability Good compatibility with other resins C ₅ hydrogenated petroleum resin and C ₉ hydrogenated petroleum resin can effectively broaden its application range.

CN201210223334.6 discloses a preparation method of C ₅ /C ₉ hydrogenated petroleum resin, the prepared C ₅ /C ₉ hydrogenated petroleum resin has light color number, moderate softening point, and compatibility with non-polar resin Excellent, widely used in the field of adhesives. Hydrogenated petroleum resin is light in color (close to colorless), odorless and tasteless, has excellent oxidation resistance, heat resistance, and UV resistance. It is the main choice to replace most existing petroleum resin applications. The main defect is that the resin saturation increases , the molecular structure does not contain polar groups, and the compatibility with polar materials is significantly reduced.

CN1813008B discloses an acid-modified petroleum resin and a hot-melt type road marking material. The acid-modified petroleum resin can improve the compatibility with polar pigments and reduce the amount of high-priced colored pigments, but the color is darker. , the taste is also greater.

CN201910079000.8 discloses an aromatically modified petroleum resin and its preparation method. The base resin is physically blended with a polar maleic anhydride copolymer and then catalytically hydrogenated to improve the stability of the petroleum resin. The obtained petroleum resin It has the advantages of light color, good compatibility, and good stability, but the introduction of polar groups can easily lead to poisoning of the catalytic hydrogenation catalyst, and the acid value of the obtained resin is low (<1.0mg KOH/g resin), which is harmful to Compatibility improvements are limited. Tackifying resins are an important component of hot-melt pressure-sensitive adhesives for labels due to their low price, acid and alkali resistance, and the advantages of better peeling force and holding power of the hot-melt pressure-sensitive adhesives prepared by them. Although the hot-melt pressure-sensitive adhesive prepared by terpene resin and natural rosin has strong cohesive force, its large odor limits its application.

In view of the above problems, it is necessary to provide a C9 hydrogenated petroleum resin with low odor, light color and good compatibility with polar materials.

Contents of the invention

The main purpose of the present invention is to provide a modified C9 hydrogenated petroleum resin, its preparation method and application, to solve the problems of existing acid-modified C9 hydrogenated petroleum resin with strong odor, deep color and compatibility with polar materials bad question.

In order to achieve the above object, the present invention provides a kind of preparation method of modified C9 hydrogenated petroleum resin on the one hand, the preparation method of this modified C9 hydrogenated petroleum resin comprises: in initiator and polar grafting activator and solvent In the presence of C9 hydrogenated petroleum resin and an acidulant for grafting reaction to obtain a grafted product system, the acidulant is an unsaturated acid anhydride and/or unsaturated acid, and the polar grafting activator is selected from cinnamate ester activators and a styrene activator; using a strong polar solvent to extract the grafted product system to obtain an extraction product, the solubility parameter of the strong polar solvent is greater than 3.0 (cal/cm ³ ) ^1/2 ; remove the solvent in the extraction product, A modified C9 hydrogenated petroleum resin is obtained.

Further, the cinnamate activator is selected from ethyl cinnamate, isopropyl cinnamate, tert-butyl cinnamate, isobutyl cinnamate, isoamyl cinnamate, isoamyl p-methoxycinnamate , Benzyl cinnamate, cinnamyl cinnamate, lauryl cinnamate, stearyl cinnamate, ethylene glycol monomethyl ether cinnamate, ethylene glycol monoethyl ether cinnamate, diethylene glycol monoethyl ether Composition of cinnamic acid, triethylene glycol monoethyl ether cinnamate, polyethylene glycol monomethyl ether cinnamate, polyethylene glycol monoethyl ether cinnamate, polyethylene glycol dilaurate and o-nitrocinnamate One or more of the group; preferably, the styrenic activator is selected from the group consisting of α-methylstyrene, o-nitrostyrene, o-methylstyrene, o-ethylstyrene, o-isopropylbenzene One or more of the group consisting of ethylene, o-tert-butylstyrene and styrene.

Further, the weight ratio of C9 hydrogenated petroleum resin, solvent, acidifying agent, initiator and polar grafting activator is 100:(20～200):(0.2～3.5):(0.01～2.0):(0.01～ 3.5).

Further, the acid value of C9 hydrogenated petroleum resin is less than 0.1, the volatile content is less than 0.15%, the Gardner color number is 0-1.0, and the aromaticity is less than 4%; the softening point is between 80-140°C; preferably, C9 The acid value of the hydrogenated petroleum resin is less than 0.08, the volatile matter content is less than 0.12%, and the Gardner color number is 0-0.1.

Further, the solvent is selected from one or more of toluene, xylene, trimethylbenzene and mineral spirits, wherein the mineral spirits are selected from saturated alkanes and/or cycloalkanes containing 6 to 12 carbon atoms; preferably, cycloalkanes The distillation range is 140-230° C.; preferably, the solvent is mineral spirits and /xylene, wherein the content of mineral spirits in the solvent is 80-100 wt%.

Further, the acidulant is selected from one or more of maleic anhydride, norbornene dioic anhydride, acrylic acid, methacrylic acid, methylnadic anhydride, 4-methyltetrahydrophthalic anhydride, citraconic anhydride and itaconic anhydride species; the initiator is selected from dibenzoyl peroxide, azobisisobutyronitrile, 2,5-dimethyl-2,5-bis-(tert-butylperoxy)hexane, 2-ethyl peroxide tert-butyl hexyl carbonate, di-tert-butyl peroxide, dicumyl peroxide, tert-butyl cumene peroxide, di-tert-butyl peroxide dicumyl peroxide, 2,2-di(tert-butyl peroxide ) butane, di-tert-amyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy(2-ethylhexanoate) and tert-butylperoxy-3,5,5-trimethylhexyl One or more of acid esters; preferably, the strong polar solvent is selected from water, acetone, butanone, cyclohexanone, N,N-dimethylformamide, N,N-dimethylacetamide, One or more of dimethyl sulfoxide, ethanol, ethylene glycol, ethylene glycol dimethyl ether and diglyme.

Further, during the grafting reaction, the polar grafting activator and/or the acidifying agent are added in batches; preferably, after the step of removing the solvent in the extraction product, the preparation method of the modified C9 hydrogenated petroleum resin also includes : adding an antioxidant to obtain a modified C9 hydrogenated petroleum resin; preferably, the weight ratio of the C9 hydrogenated petroleum resin to the antioxidant is 100:(0.1-2.0).

The second aspect of the present application also provides a modified C9 hydrogenated petroleum resin, the acid value of the modified C9 hydrogenated petroleum resin is 1-10 mgKOH/g, the Gardner color number is 0-3.0, and the voc content is lower than 0.2 %, or modified C9 hydrogenated petroleum resin is prepared by the preparation method provided by this application.

The third aspect of the present application also provides a kind of masterbatch, which is prepared by granulating the modified C9 hydrogenated petroleum resin provided by the present application as a raw material.

The fourth aspect of the application also provides a hot-melt pressure-sensitive adhesive, including a tackifying resin, and the tackifying resin includes the modified C9 hydrogenated petroleum resin provided by the application or the masterbatch provided by the application; preferably, the hot-melt The pressure-sensitive adhesive is a hot-melt pressure-sensitive adhesive for labels.

Applying the technical scheme of the present invention, adding a specific polar grafting activator during the grafting reaction can promote the grafting reaction, and effectively improve the grafting efficiency of unsaturated acid anhydride and/or unsaturated acid and modify the C9 The acid value of the hydrogenated petroleum resin can greatly improve the holding force and peel strength when used as a pressure-sensitive adhesive. On the other hand, cinnamate activators and styrene activators as graft activators can enhance the polarity of modified C9 hydrogenated petroleum resins, which is beneficial to improve the compatibility of modified C9 hydrogenated petroleum resins with polar materials. wettability and compatibility. At the same time, polar extraction with a strong polar solvent can remove small molecular substances (such as initiator residues, unreacted raw materials and polymers, etc.) that affect the odor and color in the grafted product system, thereby making the modified C9 hydrogenated Petroleum resin also has the characteristics of light color number and low voc content. In summary, the modified C9 hydrogenated petroleum resin prepared by the above method has the characteristics of light color number, low voc content and good compatibility with polar components, which can broaden the application range of C9 hydrogenated petroleum resin.

Description of drawings

The accompanying drawings constituting a part of the present application are used to provide a further understanding of the present invention, and the schematic embodiments and descriptions of the present invention are used to explain the present invention, and do not constitute an improper limitation of the present invention. In the attached picture:

Fig. 1 is the infrared spectrogram after grafting of ungrafted comparative example 1 (curve 1) and embodiment 2 (curve 2).

Fig. 2 is the infrared spectrogram of the resin prepared in Example 1 (curve A), embodiment 2 (curve B) and comparative example 1 (curve C), and the ordinate is the infrared absorption Abs of the group.

Fig. 3 is a local enlarged view of the infrared spectrum of the resin prepared in Example 1 (curve A), embodiment 2 (curve B) and comparative example 1 (curve C).

Detailed ways

It should be noted that, in the case of no conflict, the embodiments in the present application and the features in the embodiments can be combined with each other. The present invention will be described in detail below in conjunction with examples.

As described in the background technology, the existing C9 petroleum hydrogenated resin has a large odor and dark color (the C9 hydrogenated petroleum resin has no odor, and after acid modification, the voc will be very smelly if it is not removed cleanly) and is compatible with polar materials sexual problems. In order to solve the above-mentioned technical problems, the application provides a preparation method of modified C9 hydrogenated petroleum resin, the preparation method of the modified C9 hydrogenated petroleum resin comprises: in the presence of initiator and polar grafting activator and solvent Under the following conditions, the C9 hydrogenated petroleum resin and the acidifying agent are grafted to obtain a grafted product system, and the acidifying agent is an unsaturated acid anhydride or an unsaturated acid; a strong polar solvent is used to extract the grafted product system to obtain an extraction product, The solubility parameter of the strong polar solvent is greater than 3.0 (cal/cm ³ ) ^1/2 ; the solvent in the extraction product is removed to obtain the modified C9 hydrogenated petroleum resin.

Adding a specific polar grafting activator during the grafting reaction can promote the grafting reaction, and effectively improve the grafting efficiency of unsaturated acid anhydride and/or unsaturated acid and the acid value of the modified C9 hydrogenated petroleum resin , so as to greatly improve the holding force and peel strength when used as a pressure-sensitive adhesive in the future. On the other hand, cinnamate activators and styrene activators as graft activators can enhance the polarity of modified C9 hydrogenated petroleum resins, which is beneficial to improve the compatibility of modified C9 hydrogenated petroleum resins with polar materials. wettability and compatibility. At the same time, polar extraction with a strong polar solvent can remove small molecular substances (such as initiator residues, unreacted raw materials and polymers, etc.) that affect the odor and color in the grafted product system, thereby making the modified C9 hydrogenated Petroleum resin also has the characteristics of light color number and low voc content. In summary, the modified C9 hydrogenated petroleum resin prepared by the above method has the characteristics of light color number, low voc content and good compatibility with polar components, which can broaden the application range of C9 hydrogenated petroleum resin.

The term "solubility parameter" refers to a physical constant that measures the compatibility of liquid materials.

In order to further improve the activity of the grafting activator and increase the grafting rate, the types of cinnamate activators and styrene activators can be further screened. In a preferred embodiment, cinnamate activators include but are not limited to ethyl cinnamate, isopropyl cinnamate, tert-butyl cinnamate, isobutyl cinnamate, isoamyl cinnamate, p- Isoamyl Methoxycinnamate, Benzyl Cinnamate, Cinnamyl Cinnamate, Lauryl Cinnamate, Stearyl Cinnamate, Ethylene Glycol Monomethyl Ether Cinnamate, Ethylene Glycol Monoethyl Ether Cinnamate Esters, Diethylene Glycol Monoethyl Ether Cinnamate, Triethylene Glycol Monoethyl Ether Cinnamate, Polyethylene Glycol Monomethyl Ether Cinnamate, Polyethylene Glycol Monoethyl Ether Cinnamate, Polyethylene Glycol Dilaurate One or more of the group consisting of o-nitrocinnamate. Styrenic activators include, but are not limited to, alpha-methylstyrene, o-nitrostyrene, o-methylstyrene, o-ethylstyrene, o-isopropylstyrene, o-tert-butylstyrene, and styrene One or more of the group consisting of.

In a preferred embodiment, the weight ratio of C9 hydrogenated petroleum resin, solvent, acidifying agent, initiator and polar grafting activator is 100:(20～200):(0.2～3.5):(0.01～ 2.0): (0.01～3.5).

The temperature and reaction time of the grafting reaction will vary due to the types of acidifying agent, grafting activator and initiator and the amount of reaction raw materials. Preferably, the temperature of the grafting reaction is 80-200° C., and the time of the grafting reaction is 20-240 minutes, more preferably 40-70 minutes.

In a preferred embodiment, the acid value of the C9 hydrogenated petroleum resin is less than 0.1, the volatile content is less than 0.15%, the Gardner color number is 0-1.0, and the aroma is less than 4%; the softening point is between 80-140 ℃. Compared with other C9 hydrogenated petroleum resins, the selection of the above C9 hydrogenated petroleum resin is beneficial to further reduce the odor of the modified C9 hydrogenated petroleum resin and make its color lighter. More preferably, the acid value of the C9 hydrogenated petroleum resin is less than 0.08, the volatile matter content is less than 0.12%, and the Gardner color number is 0-0.1.

The solvent in the above grafting reaction process can be selected from the commonly used ones in this field. In a preferred embodiment, the solvent includes, but is not limited to, one or more of toluene, xylene, trimethylbenzene, and mineral spirits, wherein the solvent oil includes, but is not limited to, saturated alkanes and /or cycloalkanes. In order to further improve the compatibility of the reaction raw materials in the solvent, preferably, the distillation range of naphthenes is 140-230° C.; preferably, the solvent is solvent naphtha and/xylene, wherein the content of solvent naphtha in the solvent is 80-230 DEG C. 100% by weight.

In a preferred embodiment, the acidulant includes, but is not limited to, maleic anhydride, norbornene dianhydride, acrylic acid, methacrylic acid, methylnadic anhydride, 4-methyltetrahydrophthalic anhydride, citraconic anhydride, and One or more of canonic anhydrides. Compared with other acidifying agents, the above-mentioned acidifying agent has less steric hindrance and has a higher grafting rate in the grafting process, so that the modified C9 hydrogenated petroleum resin obtained has a higher acid value. It also has better holding power and peel strength during pressure sensitive adhesive application.

In the above grafting reaction process, commonly used initiators in the art can be selected. In a preferred embodiment, initiators include but are not limited to dibenzoyl peroxide, azobisisobutyronitrile, 2,5-dimethyl-2,5-bis-(tert-butylperoxy) Hexane, 2-ethylhexyl peroxide tert-butyl carbonate, di-tert-butyl peroxide, dicumyl peroxide, tert-butyl cumene peroxide, di-tert-butyl dicumyl peroxide, 2, 2-Di(tert-butylperoxy)butane, di-tert-amyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy(2-ethylhexanoate) and tert-butylperoxy-3 , One or more of 5,5-trimethylhexanoate. Compared with other initiators, the above-mentioned initiators have shorter initiation time and higher initiation efficiency.

Preferably, strong polar solvents include but are not limited to water, acetone, butanone, cyclohexanone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, ethanol, One or more of ethylene glycol, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether. The selection of the above-mentioned strong polar solvent is beneficial to further increase the small molecular substances that affect the odor and color, thereby further reducing the volatile odor of the modified C9 hydrogenated petroleum resin and making its color number lighter. More preferably, during the extraction process, the weight ratio of the C9 hydrogenated petroleum resin to the strong polar solvent is 100:(30-200).

The process of removing the solvent in the extracted product can adopt methods commonly used in the art, such as flash evaporation, distillation and the like.

In a preferred embodiment, during the grafting reaction, the polar grafting activator and/or the acidifying agent are added in batches. Adding the polar grafting activator and/or acidifying agent several times is conducive to further increasing the grafting rate and increasing the acid value of the modified C9 hydrogenated petroleum resin.

In order to improve the oxidation resistance of the modified C9 hydrogenated petroleum resin, preferably, after the step of removing the solvent in the extraction product, the preparation method of the modified C9 hydrogenated petroleum resin further includes: adding an antioxidant to obtain the modified C9 hydrogenated petroleum resin. hydrogen petroleum resin. More preferably, the weight ratio of the C9 hydrogenated petroleum resin participating in the reaction to the antioxidant is 100:(0.1-2.0).

Another aspect of the present application also provides a modified C9 hydrogenated petroleum resin, the acid value of the modified C9 hydrogenated petroleum resin is 1-10 mgKOH/g, the Gardner color number is 0-3.0, and the voc content is lower than 0.2 %, or it is prepared by the above-mentioned preparation method. The modified C9 hydrogenated petroleum resin prepared by the method has the characteristics of light color number, low voc content and good compatibility with polar components, and can broaden the application range of the C9 hydrogenated petroleum resin.

The third aspect of the present application also provides a kind of masterbatch, which is prepared by granulating the modified C9 hydrogenated petroleum resin provided by the present application as a raw material. The modified C9 hydrogenated petroleum resin and subsequent required additives are made into masterbatches, which can improve the convenience of subsequent application of the modified C9 hydrogenated petroleum resin.

The fourth aspect of the present application also provides a hot-melt pressure-sensitive adhesive, including a tackifying resin, and the tackifying resin includes the above-mentioned modified C9 hydrogenated petroleum resin or the above-mentioned masterbatch.

The modified C9 hydrogenated petroleum resin of the present invention has low voc content, low odor, light color number, and adjustable acid value, and can be used in the field of hot melt adhesives to improve C9 hydrogenated petroleum resin and polar polymers such as EVA and PU And other compatibility, promote the dispersion of petroleum resin and the interfacial force of polar materials, thereby improving the adhesion performance. The above-mentioned hot-melt pressure-sensitive adhesive is especially suitable for use as a hot-melt pressure-sensitive adhesive for labels.

The present application will be described in further detail below in conjunction with specific examples, and these examples should not be construed as limiting the scope of protection claimed in the present application.

Example 1

Use 300g of C9 hydrogenated petroleum resin HM100 with a color number of 0.1 and an aromatic content of 4% as raw material (including antioxidant), add 300g of solvent oil and preheat to 80°C until the petroleum resin is dissolved, and pour it into a 1L reaction kettle while it is hot , close the reactor, turn on the stirring, rotate at 300r/min, replace oxygen with 7atm high-purity nitrogen six times, and then raise the temperature to 160 degrees. Dissolve 3.0g of maleic anhydride, 0.6g of initiator DCP and 1.5g of α-methylstyrene in 6g of tetrahydrofuran, and press them into the reactor with 3atm nitrogen through the side feeding tank at one time, and the reaction time is 60min. Cool down to 70°C and discharge, use 100g DMF at 70°C to extract unreacted maleic anhydride and maleic anhydride polymers and other small molecules three times, solvent oil phase is flashed at 180°C and vacuum -0.085MPa to remove the solvent, A softening point of 102.0° C., an acid value of 6.4 mgKOH/g, a Gardner color number of 0.5, and a voc content of 0.12% can be obtained. Compared with Example 1, under the same conditions as other conditions, a small amount of α-methylstyrene is introduced, and the acid value of the petroleum resin grafted with maleic anhydride will be significantly improved.

Example 2

Use 300g of C9 hydrogenated petroleum resin HM100 with a color number of 0.1 and an aromatic content of 4% as raw material (including antioxidant), add 300g of solvent oil and preheat to 80°C until the petroleum resin is dissolved, and pour it into a 1L reaction kettle while it is hot , close the reactor, turn on the stirring, rotate at 300r/min, replace oxygen with 7atm high-purity nitrogen six times, and then raise the temperature to 160 degrees. Dissolve 3.0g of maleic anhydride, 0.6g of initiator DCP and 3.0g of isopropyl cinnamate in 6g of tetrahydrofuran, and press them into the reactor with 3atm nitrogen through the side feeding tank at one time, and the reaction time is 60min. Cool down to 70°C and discharge, use 100g DMF at 70°C to extract unreacted maleic anhydride and maleic anhydride polymers and other small molecules three times, solvent oil phase is flashed at 180°C and vacuum -0.085MPa to remove the solvent, A softening point of 102.5° C., an acid value of 9.5 mgKOH/g, a Gardner color number of 0.5, and a voc content of 0.12% can be obtained. Compared with Example 1, under the same other conditions, introducing 3.0 parts of isopropyl cinnamate instead of 1.5 g of α-methylstyrene will significantly increase the acid value of the maleic anhydride graft-modified petroleum resin. At the same time, isopropyl cinnamate itself has a polar ester group, which improves the compatibility with polar materials.

Example 3

Use 300g of C9 hydrogenated petroleum resin HM100 with a color number of 0.1 and an aromatic content of 4% as raw material (including antioxidant), add 300g of solvent oil and preheat to 80°C until the petroleum resin is dissolved, and pour it into a 1L reaction kettle while it is hot , close the reactor, turn on the stirring, rotate at 300r/min, replace oxygen with 7atm high-purity nitrogen six times, and then raise the temperature to 160 degrees. Dissolve 3.0g maleic anhydride, 0.6g initiator DCP and 3.0g cinnamyl cinnamate in 6g tetrahydrofuran, and press them into the reaction kettle with 3atm nitrogen through the side feeding tank at one time, and the reaction time is 60min. Cool down to 70°C and discharge, use 100g DMF at 70°C to extract unreacted maleic anhydride and maleic anhydride polymers and other small molecules three times, solvent oil phase is flashed at 180°C and vacuum -0.085MPa to remove the solvent, The softening point is 102.4°C, the acid value is 9.9mgKOH/g, the Gardner color number is 1.2, and the voc content is 0.12%. Compared with embodiment 1, under the same situation of all the other conditions, introduce 3.0 parts of cinnamyl cinnamate to replace 1.5g α-methylstyrene, two double bonds are arranged in the cinnamate structure, effectively improved grafting rate, However, it is easy to have unreacted unsaturated double bonds remaining, resulting in darker color.

Example 4

Use 300g of C9 hydrogenated petroleum resin HM100 with a color number of 0.1 and an aromatic content of 4% as raw material (including antioxidant), add 300g of solvent oil and preheat to 80°C until the petroleum resin is dissolved, and pour it into a 1L reaction kettle while it is hot , close the reactor, turn on the stirring, rotate at 300r/min, replace oxygen with 7atm high-purity nitrogen six times, and then raise the temperature to 160 degrees. Dissolve 3.0g of maleic anhydride, 0.6g of initiator DCP and 3.0g of stearyl cinnamate in 6g of tetrahydrofuran, and press them into the reactor with 3atm nitrogen through the side feeding tank at one time, and the reaction time is 60min. Cool down to 70°C and discharge, use 100g DMF at 70°C to extract unreacted maleic anhydride and maleic anhydride polymers and other small molecules three times, solvent oil phase is flashed at 180°C and vacuum -0.085MPa to remove the solvent, A softening point of 101.8° C., an acid value of 9.2 mgKOH/g, a Gardner color number of 0.6, and a voc content of 0.11% can be obtained.

Compared with Example 1, under the same other conditions, 3.0 parts of stearyl cinnamate was introduced instead of 1.5 g of α-methylstyrene. After the introduction of stearyl cinnamate as an activator, the grafting efficiency of maleic anhydride reaches more than 80%, and the acid value of the obtained modified resin is significantly improved. At the same time, the introduction of long alkyl chains also improves the fluidity and compatibility of the resin.

Example 5

Use 300g of C9 hydrogenated petroleum resin HM100 with a color number of 0.1 and an aromatic content of 4% as raw material (including antioxidant), add 300g of solvent oil and preheat to 80°C until the petroleum resin is dissolved, and pour it into a 1L reaction kettle while it is hot , close the reactor, turn on the stirring, rotate at 300r/min, replace oxygen with 7atm high-purity nitrogen six times, and then raise the temperature to 160 degrees. Dissolve 3.0g of maleic anhydride, 0.6g of initiator DCP and 3.0g of triethylene glycol monoethyl ether cinnamate in 6g of tetrahydrofuran, and press them into the reaction kettle with 3atm nitrogen through the side feeding tank at one time, and the reaction time is 60min. Cool down to 70°C and discharge, use 100g DMF at 70°C to extract unreacted maleic anhydride and maleic anhydride polymers and other small molecules three times, solvent oil phase is flashed at 180°C and vacuum -0.085MPa to remove the solvent, A softening point of 102.2° C., an acid value of 9.3 mgKOH/g, a Gardner color number of 0.5, and a voc content of 0.16% can be obtained. Compared with Example 1, under the same other conditions, 3.0 g of triethylene glycol monoethyl ether cinnamate was introduced instead of 1.5 g of α-methylstyrene.

Example 6

Use 300g of C9 hydrogenated petroleum resin HM100 with a color number of 0.1 and an aromatic content of 4% as raw material (including antioxidant), add 300g of solvent oil and preheat to 80°C until the petroleum resin is dissolved, and pour it into a 1L reaction kettle while it is hot , close the reactor, turn on the stirring, rotate at 300r/min, replace oxygen with 7atm high-purity nitrogen six times, and then raise the temperature to 160 degrees. Dissolve 3.0g maleic anhydride, 0.6g initiator DCP and 6.0g triethylene glycol monoethyl ether cinnamate in 6g tetrahydrofuran, and press them into the reaction kettle with 3atm nitrogen through the side feeding tank at one time, and the reaction time is 60min. Cool down to 70°C and discharge, use 100g DMF at 70°C to extract unreacted maleic anhydride and maleic anhydride polymers and other small molecules three times, solvent oil phase is flashed at 180°C and vacuum -0.085MPa to remove the solvent, A softening point of 102.3° C., an acid value of 9.8 mgKOH/g, a Gardner color number of 0.7, and a voc content of 0.13% can be obtained. Compared with Example 1, under the same other conditions, 6.0 g of triethylene glycol monoethyl ether cinnamate was introduced instead of 1.5 g of α-methylstyrene.

Example 7

Use 300g of C9 hydrogenated petroleum resin HM100 with a color number of 0.1 and an aromatic content of 4% as raw material (including antioxidant), add 300g of solvent oil and preheat to 80°C until the petroleum resin is dissolved, and pour it into a 1L reaction kettle while it is hot , close the reactor, turn on the stirring, rotate at 300r/min, replace oxygen with 7atm high-purity nitrogen six times, and then raise the temperature to 160 degrees. Dissolve 3.0g of maleic anhydride, 0.6g of initiator DCP and 9.0g of polyethylene glycol monoethyl ether laurate in 6g of tetrahydrofuran, and press them into the reaction kettle with 3atm nitrogen through the side feeding tank at one time, and the reaction time is 60min. Cool down to 70°C and discharge, use 100g DMF at 70°C to extract unreacted maleic anhydride and maleic anhydride polymers and other small molecules three times, solvent oil phase is flashed at 180°C and vacuum -0.085MPa to remove the solvent, A softening point of 102.3° C., an acid value of 9.8 mgKOH/g, a Gardner color number of 1.1, and a voc content of 0.16% can be obtained.

Compared with Example 1, under the same other conditions, 9.0 g of polyethylene glycol monoethyl ether laurate was introduced instead of 1.5 g of α-methylstyrene.

Example 8

Use 300g of C9 hydrogenated petroleum resin HM100 with a color number of 0.1 and an aromatic content of 4% as raw material (including antioxidant), add 300g of solvent oil and preheat to 80°C until the petroleum resin is dissolved, and pour it into a 1L reaction kettle while it is hot , close the reactor, turn on the stirring, rotate at 300r/min, replace oxygen with 7atm high-purity nitrogen six times, and then raise the temperature to 160 degrees. Dissolve 3.0g of maleic anhydride, 0.6g of initiator DCP and 3.0g of isopropyl cinnamate in 6g of tetrahydrofuran, and press them into the reactor with 3atm nitrogen through the side feeding tank at one time, and the reaction time is 30min. Cool down to 70°C and discharge, use 100g DMF at 70°C to extract unreacted maleic anhydride and maleic anhydride polymers and other small molecules three times, solvent oil phase is flashed at 180°C and vacuum -0.085MPa to remove the solvent, A softening point of 102.5° C., an acid value of 9.5 mgKOH/g, a Gardner color number of 0.5, and a voc content of 0.12% can be obtained. Compared with Example 1, under the same situation of other conditions, 3.0 parts of isopropyl cinnamate are introduced, the reaction time is shortened to 30min, and the acid value of the petroleum resin modified by maleic anhydride grafting can be significantly improved. At the same time, cinnamate itself has a polar ester group, which improves the compatibility with polar materials.

Comparative example 1

Using the unmodified C9 hydrogenated petroleum resin HM1000 as the tackifying resin, the pressure-sensitive adhesive was prepared according to the same ratio as the modified resin, and its performance was tested.

Comparative example 2

In parts by weight, 1 part of maleic anhydride and 0.2 part of initiator DCP are dissolved in 2 parts of tetrahydrofuran with 100 parts of C9 hydrogenated petroleum resin with a color number of 0.1 and an aromatic content of 4% as raw material (containing antioxidant). , mixed evenly with the resin. The homogeneously mixed petroleum resin, initiator and DCP are processed by a twin-screw extruder, the temperature of the four zones of the extruder is respectively set to 60, 150, 170, and 130°C, and the residence time is 1-2min to obtain melt-grafted petroleum Resin, softening point 101.4°C, acid value 1.7mgKOH/g; Gardner color number 2.1; voc content 0.3%. The difference from Example 1 is that the synthesis method is a twin-screw melt-grafting method. The experimental results show that the reaction time of the melt grafting method is short, resulting in low grafting efficiency, the acid value is significantly lower than that of the solution grafting method, and the unreacted residual monomers and small molecules such as initiators are difficult to remove, resulting in significant voc content Raised, the smell is great.

Comparative example 3

Use 300g of C9 hydrogenated petroleum resin HM100 with a color number of 0.1 and an aromatic content of 4% as raw material (including antioxidant), add 300g of solvent oil and preheat to 80°C until the petroleum resin is dissolved, and pour it into a 1L reaction kettle while it is hot , close the reactor, turn on the stirring, rotate at 300r/min, replace oxygen with 7atm high-purity nitrogen six times, and then raise the temperature to 160 degrees. Dissolve 3.0 g of maleic anhydride and 0.6 g of initiator DCP in 6 g of tetrahydrofuran, and press them into the reactor with 3 atm nitrogen through the side feeding tank at one time, and the reaction time is 60 min. Cool down to 70°C and discharge, use 200g water at 70°C to extract unreacted maleic anhydride and maleic anhydride polymers and other small molecules three times, solvent oil phase is flashed at 180°C and vacuum -0.085MPa to remove the solvent, A softening point of 101.5° C., an acid value of 3.7 mgKOH/g, a Gardner color number of 0.6, and a voc content of 0.14% can be obtained. The difference with Example 1 is: no grafting activator α-methylstyrene is added, and the extraction solvent adopts 200g water to replace 100g DMF in the extraction process.

Comparative example 4

Use 300g of C9 hydrogenated petroleum resin HM100 with a color number of 0.1 and an aromatic content of 4% as raw material (including antioxidant), add 300g of solvent oil and preheat to 80°C until the petroleum resin is dissolved, and pour it into a 1L reaction kettle while it is hot , close the reactor, turn on the stirring, rotate at 300r/min, replace oxygen with 7atm high-purity nitrogen six times, and then raise the temperature to 160 degrees. Dissolve 1.5g of maleic anhydride and 0.6g of initiator DCP in 6g of tetrahydrofuran, and press them into the reaction kettle with 3atm nitrogen through the side feeding tank at one time, and the reaction time is 60min. Cool down to 70°C and discharge, use 200g water at 70°C to extract unreacted maleic anhydride and maleic anhydride polymers and other small molecules three times, solvent oil phase is flashed at 180°C and vacuum -0.085MPa to remove the solvent, A softening point of 101.8° C., an acid value of 1.9 mgKOH/g, a Gardner color number of 0.4, and a voc content of 0.15% can be obtained. If the amount of maleic anhydride is reduced, the acid value of the petroleum resin grafted with maleic anhydride will decrease significantly, the Gardner color number will also decrease, and the resin color will be lighter. The difference with Example 1 is: the consumption of maleic anhydride is reduced to 1.5g by 3g, does not add grafting activator α-methylstyrene, and the extraction solvent adopts 200g water to replace 100g DMF in the extraction process.

Comparative example 5

Use 300g of C9 hydrogenated petroleum resin HM100 with a color number of 0.1 and an aromatic content of 4% as raw material (including antioxidant), add 300g of solvent oil and preheat to 80°C until the petroleum resin is dissolved, and pour it into a 1L reaction kettle while it is hot , close the reactor, turn on the stirring, rotate at 300r/min, replace oxygen with 7atm high-purity nitrogen six times, and then raise the temperature to 160 degrees. Dissolve 9.0g maleic anhydride and 0.6g initiator DCP in 6g tetrahydrofuran, and press them into the reaction kettle with 3atm nitrogen through the side feeding tank at one time, and the reaction time is 60min. Cool down to 70°C and discharge, use 200g water at 70°C to extract unreacted maleic anhydride and maleic anhydride polymers and other small molecules three times, solvent oil phase is flashed at 180°C and vacuum -0.085MPa to remove the solvent, A softening point of 101.9° C., an acid value of 7.4 mgKOH/g, a Gardner color number of 1.1, and a voc content of 0.14% can be obtained. Compared with Example 1, under the same situation of other conditions, increasing the amount of maleic anhydride added, the acid value of the petroleum resin modified by maleic anhydride grafting will improve, but the color will also deepen to a certain extent, but Gardner Shades are still small. The difference from Example 1 is that the amount of maleic anhydride is increased from 3 g to 9.0 g, no graft activator α-methylstyrene is added, and 200 g of water is used instead of 100 g of DMF as the extraction solvent during the extraction process.

Comparative example 6

Use 300g of C9 hydrogenated petroleum resin HM100 with a color number of 0.1 and an aromatic content of 4% as raw material (including antioxidant), add 300g of solvent oil and preheat to 80°C until the petroleum resin is dissolved, and pour it into a 1L reaction kettle while it is hot , close the reactor, turn on the stirring, rotate at 300r/min, replace oxygen with 7atm high-purity nitrogen six times, and then raise the temperature to 160 degrees. Dissolve 3.0g maleic anhydride and 1.2g initiator DCP in 6g tetrahydrofuran, and press them into the reaction kettle with 3atm nitrogen through the side feeding tank at one time, and the reaction time is 60min. Cool down to 70°C and discharge, use 200g water at 70°C to extract unreacted maleic anhydride and maleic anhydride polymers and other small molecules three times, solvent oil phase is flashed at 180°C and vacuum -0.085MPa to remove the solvent, It can be obtained that the softening point is 101.5° C., the acid value is 6.2 mgKOH/g; the Gardner color number is 1.7; the voc content is 0.15%. Compared with Example 1, under the same situation of all the other conditions, the addition amount of initiator DCP is doubled, and the petroleum resin acid value of maleic anhydride graft modification can significantly improve, but the color also can obviously deepen, but Gardner color Number is still small. From the results, compared with maleic anhydride, the acid value and color number of the modified petroleum resin are more sensitive to the initiator. This also provides a certain guiding significance for the formulation and process design of maleic anhydride grafted modified petroleum resin. The difference with Example 1 is: the consumption of initiator increases from 0.6g to 1.2g, does not add grafting activator α-methylstyrene, and the extraction solvent adopts 200g water to replace 100g DMF in the extraction process.

Comparative example 7

Use 300g of C9 hydrogenated petroleum resin HM100 with a color number of 0.1 and an aromatic content of 4% as raw material (including antioxidant), add 300g of solvent oil and preheat to 80°C until the petroleum resin is dissolved, and pour it into a 1L reaction kettle while it is hot , close the reactor, turn on the stirring, rotate at 300r/min, replace oxygen with 7atm high-purity nitrogen six times, and then raise the temperature to 160 degrees. Dissolve 3.0g of maleic anhydride and 0.6g of initiator DCP in 6.0g of tetrahydrofuran, and pump them into the reactor four times with a micro-metering pump when the reaction time is 0, 15, 30, and 45 minutes. The total reaction time is 60 minutes. Cool down to 70°C and discharge, use 200g water at 70°C to extract unreacted maleic anhydride and maleic anhydride polymers and other small molecules three times, solvent oil phase is flashed at 180°C and vacuum -0.085MPa to remove the solvent, A softening point of 101.5° C., an acid value of 4.8 mgKOH/g, a Gardner color number of 0.4, and a voc content of 0.16% can be obtained. Compared with Example 1, under the same other conditions, the initiator DCP and maleic anhydride are added in batches, the acid value of the maleic anhydride graft-modified petroleum resin will increase by more than 20%, and the color will be slightly lighter. The difference with Example 1 is: no grafting activator α-methylstyrene is added, the reaction raw materials are pumped in four times, and the extraction solvent adopts 200g water instead of 100g DMF in the extraction process.

Comparative example 8

Take 300g of C9 hydrogenated petroleum resin HM100 with a color number of 0.1 and an aromatic content of 4% as raw material (including antioxidant), add 300g of trimethylbenzene and preheat to 80°C until the petroleum resin is dissolved, and pour it into a 1L reaction kettle while it is hot , close the reactor, turn on the stirring, rotate at 300r/min, replace oxygen with 7atm high-purity nitrogen six times, and then raise the temperature to 160 degrees. Dissolve 3.0 g of maleic anhydride and 0.6 g of initiator DCP in 6 g of tetrahydrofuran, and press them into the reactor with 3 atm nitrogen through the side feeding tank at one time, and the reaction time is 60 min. Cool down to 70°C and discharge, use 200g water at 70°C to extract unreacted maleic anhydride and maleic anhydride polymers and other small molecules three times, solvent oil phase is flashed at 180°C and vacuum -0.085MPa to remove the solvent, A softening point of 101.5° C., an acid value of 5.0 mgKOH/g, a Gardner color number of 0.5, and a voc content of 0.14% can be obtained. Compared with Example 1, under the same situation of other conditions, trimethylbenzene is used instead of solvent oil, maleic anhydride is completely dissolved in the solvent, no grafting activator α-methylstyrene is added, and the extraction solvent adopts When 200g of water replaces 100g of DMF, the acid value of the petroleum resin grafted with maleic anhydride will increase by more than 30%, but the color will not change significantly.

Comparative example 9

Use 300g of C9 hydrogenated petroleum resin HM100 with a color number of 0.1 and an aromatic content of 4% as raw material (including antioxidant), add 300g of solvent oil and preheat to 80°C until the petroleum resin is dissolved, and pour it into a 1L reaction kettle while it is hot , close the reactor, turn on the stirring, rotate at 300r/min, replace oxygen with 7atm high-purity nitrogen six times, and then raise the temperature to 160 degrees. Dissolve 3.0 g of maleic anhydride and 0.6 g of initiator DCP in 6 g of tetrahydrofuran, and press them into the reactor with 3 atm nitrogen through the side feeding tank at one time, and the reaction time is 60 min. Cool down to 70°C and discharge, use 200g DMF at 70°C to extract unreacted maleic anhydride and maleic anhydride polymers and other small molecules three times, solvent oil phase is flashed at 180°C and vacuum -0.085MPa to remove the solvent, A softening point of 101.5° C., an acid value of 3.6 mgKOH/g, a Gardner color number of 0.6, and a voc content of 0.10% can be obtained. Compared with Example 1, no grafting activator α-methylstyrene was added, and the amount of DMF was changed from 100 g to 200 g. Using highly polar DMF instead of water for extraction, one extraction can remove most of the impurities, reduce the voc content, and the odor is smaller.

Comparative example 10

Use 300g of C9 hydrogenated petroleum resin HM100 with a color number of 0.1 and an aromatic content of 4% as raw material (including antioxidant), add 300g of solvent oil and preheat to 80°C until the petroleum resin is dissolved, and pour it into a 1L reaction kettle while it is hot , close the reactor, turn on the stirring, rotate at 300r/min, replace oxygen with 7atm high-purity nitrogen six times, and then raise the temperature to 180 degrees. Dissolve 3.0 g of maleic anhydride and 0.6 g of initiator DCP in 6 g of tetrahydrofuran, and press them into the reactor with 3 atm nitrogen through the side feeding tank at one time, and the reaction time is 60 min. Cool down to 70°C and discharge, use 200g water at 70°C to extract unreacted maleic anhydride and maleic anhydride polymers and other small molecules three times, solvent oil phase is flashed at 180°C and vacuum -0.085MPa to remove the solvent, The softening point is 101.8°C, the acid value is 4.0 mgKOH/g, the Gardner color number is 1.0, and the voc content is 0.16%. Compared with Example 1, without adding grafting activator α-methylstyrene, the reaction temperature rises to 180°C from 160°C, and the extraction solvent adopts 200g water to replace 100gDMF in the extraction process. Reaction temperature, the acid value of the petroleum resin modified by maleic anhydride grafting increases slightly, but the color number also increases, resulting in darker color. It is worth mentioning that different initiators have different optimum temperatures, and the reaction time should match the half-life of the initiator. As far as the trend is concerned, the higher the temperature, the darker the color of the grafted modified petroleum resin, which may be related to the thermal stability of the petroleum resin itself.

Comparative example 11

Use 300g of C9 hydrogenated petroleum resin HM100 with a color number of 0.1 and an aromatic content of 4% as raw material (including antioxidant), add 300g of solvent oil and preheat to 80°C until the petroleum resin is dissolved, and pour it into a 1L reaction kettle while it is hot , close the reactor, turn on the stirring, rotate at 300r/min, replace oxygen with 7atm high-purity nitrogen six times, and then raise the temperature to 160 degrees. Dissolve 3.0 g of maleic anhydride and 0.6 g of initiator DCP in 6 g of tetrahydrofuran, and press them into the reactor with 3 atm nitrogen through the side feeding tank at one time, and the reaction time is 30 min. Cool down to 70°C and discharge, use 200g water at 70°C to extract unreacted maleic anhydride and maleic anhydride polymers and other small molecules three times, solvent oil phase is flashed at 180°C and vacuum -0.085MPa to remove the solvent, A softening point of 101.5° C., an acid value of 1.8 mgKOH/g, a Gardner color number of 0.4, and a voc content of 0.15% can be obtained. Compared with Example 1, without adding grafting activator α-methylstyrene, the reaction time is reduced to 30min from 60min, and the extraction solvent adopts 200g water to replace 100g DMF in the extraction process. The results showed that the grafting rate of the product decreased and the acid value decreased. The reaction time has a significant effect on the acid value within a certain range, but if the reaction time is too long, it will often cause the color to deepen.

Atlas information:

Fig. 1 is the infrared spectrogram after grafting of ungrafted comparative example 1 (curve 1) and embodiment 2 (curve 2).

Fig. 2 is the infrared spectrogram of the resin prepared in Example 1 (curve A), embodiment 2 (curve B) and comparative example 1 (curve C), and the ordinate is the infrared absorption Abs of the group.

Fig. 3 is a local enlarged view of the infrared spectrum of the resin prepared in Example 1 (curve A), embodiment 2 (curve B) and comparative example 1 (curve C). The wave number at 1786cm ^-1 is the carbonyl absorption peak of the grafted maleic anhydride group; the wave number 1714cm ^-1 is the carbonyl absorption peak of the grafted isopropyl cinnamate. Example 2 Compared with Example 1, the 1786cm ^-1 absorption peak after grafting of maleic anhydride in curve B is stronger, and the characteristic absorption peak of the ester group characteristic peak carbonyl appears at the wavenumber 1714cm ^-1 simultaneously, which proves that cinnamic acid is Propyl esters were also grafted to C9 petroleum resins and increased the grafting rate of maleic anhydride.

The synthesis scheme and performance data of the modified C9 hydrogenated petroleum resin are shown in Table 1.

Table 1

Note: comparative example 7, the acid anhydride used and the initiator are added in four times; embodiment 1, the activator used is α-methylstyrene; embodiment 2, the activator used is isopropyl cinnamate; embodiment 3, Activator used is cinnamyl cinnamate; Embodiment 4, activator used is stearyl cinnamate; Embodiment 5, activator used is triethylene glycol monoethyl ether cinnamate; Embodiment 6, activator used It is triethylene glycol monoethyl ether cinnamate; embodiment 7, the activator used is polyethylene glycol monoethyl ether laurate. Embodiment 8, reaction time 30min. See Table 2 for a list of sources of materials used in the examples.

Table 2

Stearyl cinnamate, triethylene glycol monoethyl ether cinnamate and polyethylene glycol monoethyl ether laurate are composed of cinnamoyl chloride and the corresponding stearyl alcohol, triethylene glycol monoethyl ether and polyethylene glycol (PEG- 400) Preparation of monoethyl ether by reaction in pyridine.

In parts by weight, the classic pressure-sensitive adhesive formula is 50.0 wt% of petroleum resin; 30.0 wt% of thermoplastic elastomer SIS; 19.5 wt% of naphthenic oil; and 0.5% of antioxidant. Therefore replace C9 hydrogenated petroleum resin with acid-modified C9 hydrogenated petroleum resin to evaluate its performance, and its formula is as follows in parts by weight:

Acid-modified C9 hydrogenated petroleum resin HM1000 50wt%;

Thermoplastic elastomer SIS, grade YH1126 30%. Sinopec Baling Petrochemical Company.

Naphthenic oil KN4010, 19.5%, Xinjiang Karamay Petrochemical Company.

Additional antioxidant 1010, 0.5%, BASF AG, Germany.

The preparation method of the pressure-sensitive adhesive in the present invention: use a beaker to weigh 30% by weight of SIS elastomer YH1126, add 19.5% by weight of naphthenic oil KN4010, add 0.5% of antioxidant 1010, and use a glass rod Stir and heat to 160°C, and continue to stir for 15 minutes until the polymer is completely dissolved; add 50% by weight of acid-modified hydrogenated petroleum resin HM1000, and continue to stir at 160°C for 15 minutes to a uniform and stable solution without lumpy solids; Put the glue solution in an oven at 160°C and let it stand for 30 minutes to eliminate air bubbles. The glue solution can be used for direct coating. Coat it between the release paper and the polyethylene terephthalate (PET) film so that the thickness after drying is 30 μm, and dry it at 120° C. for 3 minutes to obtain the upper layer as the release paper, the middle layer Three-layer material release paper/pressure-sensitive adhesive/PET with pressure-sensitive adhesive as the layer and PET film as the backing, and cut it into a test object A with a width of one inch.

According to the above steps, the pressure-sensitive adhesives were prepared from the resins in Synthetic Comparative Example 1, Synthetic Comparative Examples 2-11, and Examples 1-8 in Table 1.1, as Comparative Example 1, Comparative Example 2-11 and Example 1-1. 8.

Under the conditions of temperature (23±1)°C and relative humidity (50±5)%, the release paper of test body A was peeled off to obtain a double-layer PET/pressure-sensitive adhesive. The pressure-sensitive adhesive surface of the PET/pressure-sensitive adhesive double-layer material is closely adhered to a standard stainless steel plate to obtain a PET/pressure-sensitive adhesive/stainless steel plate three-layer material. Then by rolling three times under the conditions of 0.25MPa and 300mm/min, the pressure-sensitive adhesive and the stainless steel plate are tightly adhered together to prepare the standard sample for the peel strength test.

Test the peel strength according to GBT 2792-2014, the test conditions are as follows: temperature: (23±1)℃, relative humidity (50±5)%, glass angle, 180o; peel test tensile rate: 300mm/min. Universal testing machine manufacturer, Japan Shimadzu Corporation.

Under the conditions of temperature (23±1)°C and relative humidity (50±5)%, the release paper of test body A was peeled off to obtain a double-layer PET/pressure-sensitive adhesive. The pressure-sensitive adhesive surface of the PET/pressure-sensitive adhesive double-layer material is gently attached to the standard stainless steel plate to prepare the Loop tack test standard sample.

The initial tack of the pressure-sensitive adhesive is measured by the Loop tack test method, and the test temperature is (23±1)°C. The equipment used in the Loop tack is the LT-1000 Loop Belt Initial Adhesion Tester, produced by American ChemInstruments.

Under the conditions of temperature (23±1)°C and relative humidity (50±5)%, the release paper of test body A was peeled off to obtain a double-layer material PET/pressure-sensitive adhesive, which can be used for pressure-sensitive adhesive stickiness test. Pressure-sensitive adhesive stickiness test standard: GBT4851-2014 measurement, test temperature: 40°C. Saicheng Instrument holds viscosity tester, model CZY-8S, weight (1000±5) g.

The release paper used in the present invention has a thickness of 50 μm, and the manufacturer is Dongxin Composite Material Co., Ltd.

The PET film used in the present invention has a thickness of 50 μm, and the manufacturer is Ningbo Longyang Technology Co., Ltd.

The used coating machine of the present invention is the Hot Melt Lab Coater Laminater/HLCL-1000 coating machine of U.S. ChemInstruments company.

The above-mentioned acid-modified light-colored, low-odor C9 hydrogenated petroleum resin was used to prepare pressure-sensitive adhesives according to the above-mentioned formula, and the ring adhesion, holding power and peel strength were tested according to the above-mentioned test methods. The results are shown in Table 3.

table 3

It can be seen from Table 3 that as the acid value increases, the holding force and peel strength are significantly improved, because more acid anhydride or carboxyl groups can form chemical bonds with the metal surface to improve the adhesion effect.

Compared with Comparative Examples 1, 2 and 3, the initial adhesion of the hot melt adhesive prepared by grafting modified C9 hydrogenated petroleum resin is significantly improved, and the peel strength is also positively correlated with the acid value.

From the comparison of Comparative Example 3 and Examples 1-8, it can be found that the introduction of preferred grafting activators such as α-methylstyrene, isopropyl cinnamate, stearyl cinnamate, triethylene glycol Monoethyl ether cinnamate, etc., can promote the grafting reaction of maleic anhydride, thereby improving the grafting efficiency of maleic anhydride and the acid value of C9 hydrogenated petroleum resin, and improving the holding force and peel strength of pressure-sensitive adhesives important role.

In conjunction with Comparative Example 3 and Comparative Example 11, from the comparison of Example 2 and Example 8, it can be found that after introducing the grafting activator isopropyl cinnamate, the grafting reaction time is shortened from 60min to 30min, reducing the amount of resin The color number decreases with the residence time at high temperature. Other performance indexes change very little, which can improve production efficiency while ensuring product quality in industrial production.

It can be seen from Examples 4 and 7 that the introduction of long-chain alkyl groups improves the fluidity of the modified C9 hydrogenated petroleum resin, and significantly improves the ring initial adhesion of the pressure-sensitive adhesive.

The introduction of polar ester monomers, especially cinnamate compounds containing multiple ether bonds, also significantly increases the polarity of the resin, thereby improving the wettability with polar materials and improving the performance of pressure-sensitive adhesives. stickiness.

Embodiment 3, comparative example 5 and comparative example 1 are compared, under the situation that keeps color number and smell not to increase substantially, initial adhesion strength has been promoted respectively by 34% and 25%, peel strength has promoted respectively 25% and 14.4, but keeps Viscosity did not increase significantly. The introduction of acid anhydride groups and polar ester groups that can participate in chemical reactions, especially the introduction of ester groups containing long-chain alkyl groups, can significantly improve the initial adhesion and peel strength. The two complement each other and play a role. to a certain synergy.

From the above description, it can be seen that the above-mentioned embodiments of the present invention have achieved the following technical effects: use a strong polar solvent to extract small molecular substances that affect odor and color, reduce the voc content, and prepare acid-modified C9 with little odor. Hydrogenated petroleum resin. In the grafting reaction process, a grafting activator is introduced, which can significantly improve the grafting efficiency and grafting rate of the acidifying agent, and can reduce the amount of initiator or reduce the reaction time, which is beneficial to the reduction of acid-modified C9 hydrogenated petroleum resin. Color and improve production efficiency play an important role. Applying the technical scheme of the present invention, adding a specific polar grafting activator during the grafting reaction can promote the grafting reaction, and effectively improve the grafting efficiency of unsaturated acid anhydride and/or unsaturated acid and modify the C9 The acid value of the hydrogenated petroleum resin can greatly improve the holding force and peel strength when used as a pressure-sensitive adhesive. On the other hand, cinnamate activators all contain polar groups, and using them as grafting activators can improve the polarity of modified C9 hydrogenated petroleum resins, which is beneficial to improve the polarity of modified C9 hydrogenated petroleum resins. Wetting and compatibility with polar materials. At the same time, polar extraction with a strong polar solvent can remove small molecular substances (such as initiator residues, unreacted raw materials and polymers, etc.) that affect the smell and color in the grafted product system, thereby making the modified C9 hydrogenated Petroleum resin also has the characteristics of light color number and low voc content. In summary, the modified C9 hydrogenated petroleum resin prepared by the above method has the characteristics of light color, low voc content and good compatibility with polar components, which can broaden the application of C9 hydrogenated petroleum resin.

It should be noted that the terms "first" and "second" in the specification and claims of the present application are used to distinguish similar objects, but not necessarily used to describe a specific order or sequence. It is to be understood that the terms so used are interchangeable under appropriate circumstances such that the embodiments of the application described herein are, for example, capable of operation in sequences other than those described herein.

The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims (10)

1. A preparation method of modified C9 hydrogenated petroleum resin is characterized by comprising the following steps:

in the presence of an initiator, a polar grafting activator and a solvent, carrying out grafting reaction on the C9 hydrogenated petroleum resin and an acidifier to obtain a grafting product system, wherein the acidifier is unsaturated anhydride and/or unsaturated acid, and the polar grafting activator is selected from cinnamate activators and styrene activators;

extracting the grafted product system with a strongly polar solvent having a solubility parameter greater than 3.0 (cal/cm) to obtain an extracted product ³ ) ^1/2 ；

And removing the solvent in the extraction product to obtain the modified C9 hydrogenated petroleum resin.

2. The method of claim 1, wherein the cinnamate activator is one or more selected from the group consisting of ethyl cinnamate, isopropyl cinnamate, tert-butyl cinnamate, isobutyl cinnamate, isoamyl p-methoxycinnamate, benzyl cinnamate, cinnamyl cinnamate, dodecyl cinnamate, octadecyl cinnamate, ethylene glycol monomethyl ether cinnamate, ethylene glycol monoethyl ether cinnamate, diethylene glycol monoethyl ether cinnamate, triethylene glycol monoethyl ether cinnamate, polyethylene glycol monomethyl ether cinnamate, polyethylene glycol monoethyl ether cinnamate, polyethylene glycol dilaurate, and o-nitro cinnamate;

preferably, the styrenic activator is selected from one or more of the group consisting of α -methylstyrene, o-nitrostyrene, o-methylstyrene, o-ethylstyrene, o-isopropylstyrene, o-tert-butylstyrene and styrene.

3. The process for the preparation of a modified C9 hydrogenated petroleum resin, according to claim 1 or 2, wherein the weight ratio of said C9 hydrogenated petroleum resin, said solvent, said acidifying agent, said initiator and said polar grafting activator is 100:

(20～200)：(0.2～3.5)：(0.01～2.0)：(0.01～3.5)。

4. the method for preparing modified C9 hydrogenated petroleum resin according to claim 1, wherein the C9 hydrogenated petroleum resin has an acid value of less than 0.1, a volatile content of less than 0.15%, a Gardner color number of 0 to 1.0, and an aromaticity of less than 4%; the softening point is between 80 and 140 ℃;

preferably, the acid value of the C9 hydrogenated petroleum resin is less than 0.08, the volatile content is less than 0.12 percent, and the Gardner color number is 0-0.1.

5. The method for preparing modified C9 hydrogenated petroleum resin according to claim 1, wherein said solvent is selected from one or more of toluene, xylene, trimethylbenzene and mineral spirits, wherein said mineral spirits are selected from saturated alkanes and/or cycloalkanes containing 6 to 12 carbon atoms;

preferably, the distillation range of the cycloalkane is 140 to 230 ℃;

preferably, the solvent is solvent oil and/or xylene, wherein the content of the solvent oil in the solvent is 80-100 wt%.

6. The method of claim 1, wherein the acidifying agent is one or more selected from the group consisting of maleic anhydride, nadic anhydride, acrylic acid, methacrylic acid, nadic methyl anhydride, 4-methyl tetrahydrophthalic anhydride, citraconic anhydride, and itaconic anhydride;

the initiator is selected from one or more of dibenzoyl peroxide, azobisisobutyronitrile, 2,5-dimethyl-2,5-bis- (tert-butylperoxy) hexane, tert-butyl peroxy-2-ethylhexyl carbonate, di-tert-butyl peroxide, dicumyl peroxide, tert-butylcumyl peroxide, di-tert-butylperoxydicumyl peroxide, 2,2-di (tert-butylperoxy) butane, di-tert-amyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy (2-ethylhexanoate) and tert-butylperoxy-3,5,5-trimethyl hexanoate;

preferably, the strong polar solvent is one or more selected from water, acetone, butanone, cyclohexanone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, ethanol, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether.

7. The process for the preparation of modified C9 hydrogenated petroleum resin according to claim 1, wherein said polar grafting activator and/or said acidifying agent are added in portions during the grafting reaction;

preferably, the method for preparing the modified C9 hydrogenated petroleum resin further comprises, after the step of removing the solvent from the extraction product: adding an antioxidant to obtain the modified C9 hydrogenated petroleum resin; preferably, the weight ratio of the C9 hydrogenated petroleum resin to the antioxidant is 100 (0.1-2.0).

8. A modified C9 hydrogenated petroleum resin, characterized in that the acid value of the modified C9 hydrogenated petroleum resin is 1 to 10mgKOH/g, gardner color number is 0 to 3.0, voc content is less than 0.2%, or the modified C9 hydrogenated petroleum resin is prepared by the preparation method according to any one of claims 1 to 7.

9. A masterbatch, which is prepared by granulating the modified C9 hydrogenated petroleum resin of claim 8.

10. A hot-melt pressure-sensitive adhesive comprising a tackifying resin, wherein the tackifying resin comprises the modified C9 hydrogenated petroleum resin of claim 8 or the masterbatch of claim 9; preferably, the hot melt pressure sensitive adhesive is a hot melt pressure sensitive adhesive for labels.

Images