CN115975132A - Modified C9 hydrogenated petroleum resin, preparation method and application thereof - Google Patents
Modified C9 hydrogenated petroleum resin, preparation method and application thereof Download PDFInfo
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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
Technical Field
The invention relates to the field of preparation of modified C9 hydrogenated petroleum resin, and particularly relates to modified C9 hydrogenated petroleum resin, a preparation method and application thereof.
Background
The petroleum resin is C byproduct in petroleum cracking process 5 Fraction, C 9 One or more of fractions rich in unsaturated olefin such as fractions are mixed as raw materials to produce the thermoplastic resin through processes such as pretreatment, polymerization, distillation and the like. The aliphatic resin (C) is classified into aliphatic resins according to the difference of raw materials 5 ) Alicyclic resin (DCPD) and aromatic resin (C) 9 ) Aliphatic/aromatic copolymer resin (C) 5 /C 9 )、C 5 Hydrogenated Petroleum resins and C 9 Hydrogenated petroleum resin. Petroleum resin has low price, low melting point and good water resistance and is widely used in the fields of hot melt adhesives, pressure-sensitive adhesives, rubber, paints, printing ink and the like, but petroleum resin contains a large amount of unsaturated bonds and does not contain polar groups, and the petroleum resin prepared by a thermal polymerization process has the advantages of deep color, poor thermal stability, large smell and poor compatibility with polar materials. Will C 5 And C 9 Catalytic hydrogenation of double bond and aromatic ring in petroleum resinModifying, removing residual halide in the polymerization process of the resin, improving the photo-thermal stability of the product, and obtaining C with light color number, good thermal stability and good compatibility with other resins 5 Hydrogenated Petroleum resins and C 9 The hydrogenated petroleum resin can effectively widen the application range.
CN201210223334.6 discloses a C 5 /C 9 Preparation method of hydrogenated petroleum resin and C prepared by method 5 /C 9 The hydrogenated petroleum resin has a light color number, a moderate softening point and excellent compatibility with non-polar resin, and has wide application in the field of adhesives. Hydrogenated petroleum resin is light in color (can be close to colorless), odorless, tasteless, oxidation-resistant, heat-resistant and ultraviolet-resistant, is a main choice for replacing most of the existing petroleum resins, and has the main defects that the resin saturation degree is increased, the molecular structure does not contain polar groups, and the compatibility with polar materials is obviously reduced.
CN1813008B discloses an acid-modified petroleum resin which can improve compatibility with polar pigments and reduce the amount of expensive coloring pigments, but has a darker color and a larger taste, and a hot-melt type material for marking a pavement marking.
CN201910079000.8 discloses an aromatic modified petroleum resin and a preparation method thereof, wherein a base resin and a polar maleic anhydride copolymer are physically blended and then subjected to catalytic hydrogenation, so that the stability of the petroleum resin is improved, and the prepared petroleum resin has the advantages of light color, good compatibility, good stability and the like, but the introduction of a polar group easily causes catalytic hydrogenation catalyst poisoning, and the obtained resin has a low acid value (less than 1.0mg KOH/g resin) and is limited in compatibility improvement. The tackifying resin has the advantages of low price, acid resistance and alkali resistance, and the hot-melt pressure-sensitive adhesive prepared from the tackifying resin has better stripping force and holding power, and is an important component of the hot-melt pressure-sensitive adhesive for the label. The hot melt pressure sensitive adhesive prepared from terpene resin and natural rosin has strong adhesive force, but the application of the hot melt pressure sensitive adhesive is greatly limited by the odor.
In view of the above problems, it is desirable to provide a C9 hydrogenated petroleum resin having a low odor, a light color, and good compatibility with polar materials.
Disclosure of Invention
The invention mainly aims to provide a modified C9 hydrogenated petroleum resin, a preparation method and application thereof, and aims to solve the problems of strong smell, dark color and poor compatibility with polar materials of the existing acid modified C9 hydrogenated petroleum resin.
In order to achieve the above object, one aspect of the present invention provides a method for preparing a modified C9 hydrogenated petroleum resin, the method comprising: 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.
Further, the cinnamate-based activator is selected from one or more of 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 alpha-methylstyrene, o-nitrostyrene, o-methylstyrene, o-ethylstyrene, o-isopropylstyrene, o-tert-butylstyrene and styrene.
Further, the weight ratio of the C9 hydrogenated petroleum resin, the solvent, the acidifier, the initiator and the polar grafting activator is 100: (20-200): (0.2-3.5): (0.01-2.0): (0.01-3.5).
Furthermore, the acid value of the C9 hydrogenated petroleum resin is less than 0.1, the volatile content is less than 0.15 percent, the Gardner color number is 0-1.0, and the aromaticity is less than 4 percent; 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.
Further, the solvent is one or more selected from toluene, xylene, trimethylbenzene and solvent oil, wherein the solvent oil is selected from saturated alkane and/or cycloalkane containing 6 to 12 carbon atoms; preferably, the distillation range of the cycloalkane is 140 to 230 ℃; preferably, the solvent is mineral spirit and/or xylene, wherein the content of the mineral spirit in the solvent is 80 to 100wt%.
Further, the acidifying agent is selected from one or more of maleic anhydride, nadic anhydride, acrylic acid, methacrylic acid, methyl nadic 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-butylperoxy-dicumyl 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.
Further, during the grafting reaction, the polar grafting activator and/or the acidifying agent are added in portions; 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 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 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, the voc content is lower than 0.2%, or the modified C9 hydrogenated petroleum resin is prepared by the preparation method provided by the application.
The third aspect of the application also provides a master batch, which is prepared by taking the modified C9 hydrogenated petroleum resin provided by the application as a raw material and granulating the raw material.
The fourth aspect of the application also provides a hot-melt pressure-sensitive adhesive, which comprises tackifying resin, wherein the tackifying resin comprises the modified C9 hydrogenated petroleum resin or the master batch provided by the application; preferably, the hot melt pressure sensitive adhesive is a hot melt pressure sensitive adhesive for labels.
By applying the technical scheme of the invention, the specific polar grafting activating agent is added in the grafting reaction process to promote the grafting reaction, and the grafting efficiency of unsaturated anhydride and/or unsaturated acid and the acid value of the modified C9 hydrogenated petroleum resin are effectively improved, so that the permanent adhesion and the peel strength when the modified C9 hydrogenated petroleum resin is used as a pressure-sensitive adhesive in the follow-up process can be greatly improved. On the other hand, the polarity of the modified C9 hydrogenated petroleum resin can be improved by taking the cinnamate type activating agent and the styrene type activating agent as grafting activating agents, so that the wettability and compatibility of the modified C9 hydrogenated petroleum resin and a polar material are improved. Meanwhile, the polar extraction of the strong polar solvent can remove small molecular substances (such as initiator residues, unreacted raw materials, polymers and the like) which influence the smell and the color in a grafting product system, so that the prepared modified C9 hydrogenated petroleum resin also has the characteristics of light color number, low voc content and the like. In conclusion, 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 widen the application range of the C9 hydrogenated petroleum resin.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate embodiment(s) of the invention and together with the description serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 shows the IR spectra after grafting of comparative example 1 (curve 1) and example 2 (curve 2) without grafting.
FIG. 2 is an infrared spectrum of resins prepared in example 1 (curve A), example 2 (curve B) and comparative example 1 (curve C) with the ordinate being the infrared absorption Abs of the radicals.
FIG. 3 is a partial magnified view of the IR spectra of the resins prepared in example 1 (curve A), example 2 (curve B) and comparative example 1 (curve C).
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As described in the background art, the existing C9 petroleum hydrogenated resin has the problems of strong odor, dark color (C9 hydrogenated petroleum resin has no odor, and the odor is large when voc is not removed cleanly after acid modification) and poor compatibility with polar materials. In order to solve the technical problems, the application provides a preparation method of a modified C9 hydrogenated petroleum resin, and 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 or unsaturated acid; 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 specific polar grafting activating agent is added in the grafting reaction process to promote the grafting reaction, effectively improve the grafting efficiency of unsaturated anhydride and/or unsaturated acid and the acid value of the modified C9 hydrogenated petroleum resin, and greatly improve the permanent adhesion and peel strength when the modified C9 hydrogenated petroleum resin is used as a pressure-sensitive adhesive. On the other hand, the polarity of the modified C9 hydrogenated petroleum resin can be improved by taking the cinnamate type activating agent and the styrene type activating agent as grafting activating agents, so that the wettability and compatibility of the modified C9 hydrogenated petroleum resin and a polar material are improved. Meanwhile, the polar extraction of the strong polar solvent can remove small molecular substances (such as initiator residues, unreacted raw materials, polymers and the like) which influence the smell and the color in a grafting product system, so that the prepared modified C9 hydrogenated petroleum resin also has the characteristics of light color number, low voc content and the like. In conclusion, 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 widen the application range of the C9 hydrogenated petroleum resin.
The term "solubility parameter" refers to a physical constant that measures the miscibility of a liquid material.
In order to further improve the activity of the grafting activator and the grafting rate, the types of the cinnamate type activator and the styrene type activator can be further screened. In a preferred embodiment, the cinnamate based activator includes, but is not limited to, one or more of the group consisting of ethyl cinnamate, isopropyl cinnamate, t-butyl cinnamate, isobutyl 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 cinnamate, triethylene glycol monoethyl ether cinnamate, polyethylene glycol monomethyl ether cinnamate, polyethylene glycol monoethyl ether cinnamate, polyethylene glycol dilaurate, and o-nitrocinnamate. Styrenic activators include, but are not limited to, one or more of the group consisting of alpha-methylstyrene, o-nitrostyrene, o-methylstyrene, o-ethylstyrene, o-isopropylstyrene, o-tert-butylstyrene, and styrene.
In a preferred embodiment, the weight ratio of C9 hydrogenated petroleum resin, solvent, acidulant, 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 vary depending on the kinds of the acidifying agent, the grafting activator and the initiator and the amount of the reaction raw materials. Preferably, the temperature of the grafting reaction is 80 to 200 ℃ and the time of the grafting reaction is 20 to 240min, more preferably 40 to 70min.
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 aromaticity is less than 4%; the softening point is between 80 and 140 ℃. Compared with other C9 hydrogenated petroleum resins, the C9 hydrogenated petroleum resin is favorable for further reducing the odor of the prepared modified C9 hydrogenated petroleum resin and lightening the color of the modified C9 hydrogenated petroleum resin. More preferably, the acid value of the C9 hydrogenated petroleum resin is less than 0.08, the volatile content is less than 0.12%, and the Gardner color number is 0 to 0.1.
The solvent used in the grafting reaction may be any one commonly used in the art. In a preferred embodiment, the solvent includes, but is not limited to, one or more of toluene, xylene, trimethylbenzene, and solvent oils, wherein the solvent oils include, but are not limited to, saturated alkanes and/or cycloalkanes having from 6 to 12 carbon atoms. In order to further improve the compatibility of the reaction raw materials in the solvent, the distillation range of the cycloalkane is preferably 140-230 ℃; preferably, the solvent is mineral spirit and/or xylene, wherein the content of the mineral spirit in the solvent is 80 to 100wt%.
In a preferred embodiment, the acidifying agent includes, but is not limited to, one or more of maleic anhydride, nadic anhydride, acrylic acid, methacrylic acid, methyl nadic anhydride, 4-methyl tetrahydrophthalic anhydride, citraconic anhydride, and itaconic anhydride. Compared with other acidifiers, the acidifier has smaller steric hindrance and higher grafting rate in the grafting process, so that the prepared modified C9 hydrogenated petroleum resin has higher acid value and better permanent adhesion and peel strength in the subsequent application process of the pressure-sensitive adhesive.
The above grafting reaction may be carried out by using an initiator of the kind commonly used in the art. In a preferred embodiment, the initiator includes, but is not limited to, one or more of dibenzoyl peroxide, azobisisobutyronitrile, 2,5-dimethyl-2,5-bis- (t-butylperoxy) hexane, t-butyl peroxy 2-ethylhexyl carbonate, di-t-butyl peroxide, dicumyl peroxide, t-butyl cumyl peroxide, di-t-butylperoxydicumyl, 2,2-di (t-butylperoxy) butane, di-t-amyl peroxide, t-butyl peroxybenzoate, t-butyl peroxy (2-ethylhexanoate), and t-butylperoxy-3,5,5-trimethylhexanoate. Compared with other initiators, the initiators have shorter initiation time and higher initiation efficiency.
Preferably, the strongly polar solvent includes, but is not limited to, one or more of water, acetone, butanone, cyclohexanone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, ethanol, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether. The strong polar solvent is favorable for further improving small molecular substances influencing the smell and the color, so that the volatile smell of the modified C9 hydrogenated petroleum resin is further reduced, and the color number of the modified C9 hydrogenated petroleum resin is lighter. More preferably, the weight ratio of the C9 hydrogenated petroleum resin to the strong polar solvent in the extraction process is 100 (30-200).
The solvent in the extraction product can be removed by methods commonly used in the art, such as flash evaporation, distillation, etc.
In a preferred embodiment, the polar grafting activator and/or acidifying agent is added in portions during the grafting reaction. The polar grafting activating agent and/or the acidifying agent are added for multiple times, so that the grafting rate is further improved, and the acid value of the modified C9 hydrogenated petroleum resin is improved.
In order to improve the oxidation resistance of the modified C9 hydrogenated petroleum resin, preferably, the preparation method of 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. More preferably, the weight ratio of the C9 hydrogenated petroleum resin to the antioxidant participating in the reaction is 100: (0.1-2.0).
The 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 the modified C9 hydrogenated petroleum resin is prepared by the 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 widen the application range of the C9 hydrogenated petroleum resin.
The third aspect of the application also provides a master batch, which is prepared by taking the modified C9 hydrogenated petroleum resin provided by the application as a raw material and granulating the raw material. The modified C9 hydrogenated petroleum resin and the additives required subsequently are prepared into master batches, so that the convenience of the subsequent application of the modified C9 hydrogenated petroleum resin can be improved.
The fourth aspect of the application also provides a hot-melt pressure-sensitive adhesive, which comprises tackifying resin, wherein the tackifying resin comprises the modified C9 hydrogenated petroleum resin or the master batch.
The modified C9 hydrogenated petroleum resin has low voc content, small smell, light color number and adjustable acid value, can be used in the field of hot melt adhesives, improves the compatibility of the C9 hydrogenated petroleum resin and polar polymers such as EVA, PU and the like, promotes the dispersion of the petroleum resin and the interface acting force of polar materials, and further improves the adhesive property. The hot-melt pressure-sensitive adhesive is particularly suitable for being used as a hot-melt pressure-sensitive adhesive for labels.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Example 1
300g of C9 hydrogenated petroleum resin HM100 with color number of 0.1 and aromatic hydrocarbon content of 4 percent is taken as a raw material (containing an antioxidant), 300g of solvent oil is added, the mixture is preheated to 80 ℃ until the petroleum resin is dissolved, the mixture is poured into a 1L reaction kettle while the mixture is hot, the reaction kettle is closed, stirring is started, the rotating speed is 300r/min, high-purity nitrogen with the pressure of 7atm is used for six times to remove oxygen, and then the temperature is raised to 160 ℃. 3.0g of maleic anhydride, 0.6g of initiator DCP and 1.5g of alpha-methylstyrene are dissolved in 6g of tetrahydrofuran and pressed into the reaction vessel in one portion through a side feed vessel with 3atm of nitrogen for a reaction time of 60min. Cooling to 70 deg.C, discharging, extracting unreacted maleic anhydride and maleic anhydride polymer with 70 deg.C 100g DMF for three times, and removing solvent by flash evaporation at 180 deg.C and vacuum degree of-0.085 MPa to obtain a solvent oil phase with softening point of 102.0 deg.C and acid value of 6.4mgKOH/g; gardner color number 0.5; the voc content was 0.12%. Compared with the example 1, under the same conditions, the acid value of the petroleum resin grafted and modified by maleic anhydride is obviously improved by introducing a small amount of alpha-methyl styrene.
Example 2
300g of C9 hydrogenated petroleum resin HM100 with color number of 0.1 and aromatic hydrocarbon content of 4 percent is taken as a raw material (containing an antioxidant), 300g of solvent oil is added, the mixture is preheated to 80 ℃ until the petroleum resin is dissolved, the mixture is poured into a 1L reaction kettle while the mixture is hot, the reaction kettle is closed, stirring is started, the rotating speed is 300r/min, high-purity nitrogen with the pressure of 7atm is used for six times to remove oxygen, and then the temperature is raised to 160 ℃. 3.0g of maleic anhydride, 0.6g of initiator DCP and 3.0g of isopropyl cinnamate are dissolved in 6g of tetrahydrofuran, and the mixture is pressed into a reaction kettle at one time through a side feeding tank by using 3atm nitrogen, and the reaction time is 60min. Cooling to 70 deg.C, discharging, extracting unreacted maleic anhydride and maleic anhydride polymer with 70 deg.C 100g DMF for three times, and removing solvent by flash evaporation at 180 deg.C and vacuum degree of-0.085 MPa to obtain a solvent oil phase with softening point of 102.5 deg.C and acid value of 9.5mgKOH/g; gardner color number 0.5; the voc content was 0.12%. Compared with example 1, under the same conditions, the acid value of the petroleum resin grafted and modified by maleic anhydride is obviously improved by introducing 3.0 parts of isopropyl cinnamate instead of 1.5g of alpha-methyl styrene. Meanwhile, isopropyl cinnamate has a polar ester group, so that the compatibility with a polar material is improved.
Example 3
300g of C9 hydrogenated petroleum resin HM100 with color number of 0.1 and aromatic hydrocarbon content of 4 percent is taken as a raw material (containing an antioxidant), 300g of solvent oil is added, the mixture is preheated to 80 ℃ until the petroleum resin is dissolved, the mixture is poured into a 1L reaction kettle while the mixture is hot, the reaction kettle is closed, stirring is started, the rotating speed is 300r/min, high-purity nitrogen with the pressure of 7atm is used for six times to remove oxygen, and then the temperature is raised to 160 ℃. 3.0g of maleic anhydride, 0.6g of initiator DCP and 3.0g of cinnamyl cinnamate are dissolved in 6g of tetrahydrofuran, and the dissolved substances are pressed into a reaction kettle in one step by using nitrogen with the pressure of 3atm through a side feeding tank for reaction for 60min. Cooling to 70 deg.C, discharging, extracting unreacted maleic anhydride and maleic anhydride polymer with 70 deg.C 100g DMF for three times, and removing solvent by flash evaporation at 180 deg.C and vacuum degree of-0.085 MPa to obtain a solvent oil phase with softening point of 102.4 deg.C and acid value of 9.9mgKOH/g; gardner color number 1.2; the voc content was 0.12%. Compared with the example 1, under the same conditions, 3.0 parts of cinnamyl cinnamate is introduced to replace 1.5g of alpha-methyl styrene, and the cinnamyl cinnamate has two double bonds in the structure, so that the grafting rate is effectively improved, but unreacted unsaturated double bonds are easy to remain, and the color is deepened.
Example 4
300g of C9 hydrogenated petroleum resin HM100 with color number of 0.1 and aromatic hydrocarbon content of 4% is used as a raw material (containing an antioxidant), 300g of solvent oil is added to preheat to 80 ℃ until the petroleum resin is dissolved, the mixture is poured into a 1L reaction kettle while the mixture is hot, the reaction kettle is closed, stirring is started, the rotating speed is 300r/min, high-purity nitrogen of 7atm is used for replacing for six times to remove oxygen, and then the temperature is raised to 160 ℃. 3.0g of maleic anhydride, 0.6g of initiator DCP and 3.0g of octadecyl cinnamate are dissolved in 6g of tetrahydrofuran, and the solution is pressed into a reaction kettle at one time through a side feeding tank by using 3atm nitrogen, and the reaction time is 60min. Cooling to 70 deg.C, discharging, extracting unreacted maleic anhydride and maleic anhydride polymer with 70 deg.C 100g DMF for three times, and removing solvent by flash evaporation at 180 deg.C and vacuum degree of-0.085 MPa to obtain a solution with softening point of 101.8 deg.C and acid value of 9.2mgKOH/g; gardner color number 0.6; the voc content was 0.11%.
In the same conditions as in example 1, 3.0 parts of stearyl cinnamate were introduced instead of 1.5g of a-methylstyrene. After the activator octadecyl cinnamate is introduced, the grafting efficiency of maleic anhydride reaches more than 80 percent, and the acid value of the obtained modified resin is obviously improved. Meanwhile, the introduction of the long alkyl chain also improves the fluidity and compatibility of the resin.
Example 5
300g of C9 hydrogenated petroleum resin HM100 with color number of 0.1 and aromatic hydrocarbon content of 4 percent is taken as a raw material (containing an antioxidant), 300g of solvent oil is added, the mixture is preheated to 80 ℃ until the petroleum resin is dissolved, the mixture is poured into a 1L reaction kettle while the mixture is hot, the reaction kettle is closed, stirring is started, the rotating speed is 300r/min, high-purity nitrogen with the pressure of 7atm is used for six times to remove oxygen, and then the temperature is raised to 160 ℃. 3.0g of maleic anhydride, 0.6g of initiator DCP and 3.0g of triethylene glycol monoethyl ether cinnamate are dissolved in 6g of tetrahydrofuran, and the mixture is pressed into a reaction kettle at one time through a side feeding tank by using 3atm nitrogen, and the reaction time is 60min. Cooling to 70 deg.C, discharging, extracting unreacted maleic anhydride and maleic anhydride polymer with 70 deg.C 100g DMF for three times, and removing solvent by flash evaporation at 180 deg.C and vacuum degree of-0.085 MPa to obtain a solvent oil phase with softening point of 102.2 deg.C and acid value of 9.3mgKOH/g; gardner color number 0.5; the voc content was 0.16%. In the same conditions as in example 1, 3.0g of triethylene glycol monoethyl ether cinnamate was introduced instead of 1.5g of alpha-methylstyrene.
Example 6
300g of C9 hydrogenated petroleum resin HM100 with color number of 0.1 and aromatic hydrocarbon content of 4 percent is taken as a raw material (containing an antioxidant), 300g of solvent oil is added, the mixture is preheated to 80 ℃ until the petroleum resin is dissolved, the mixture is poured into a 1L reaction kettle while the mixture is hot, the reaction kettle is closed, stirring is started, the rotating speed is 300r/min, high-purity nitrogen with the pressure of 7atm is used for six times to remove oxygen, and then the temperature is raised to 160 ℃. 3.0g of maleic anhydride, 0.6g of initiator DCP and 6.0g of triethylene glycol monoethyl ether cinnamate were dissolved in 6g of tetrahydrofuran and were pressed into the reaction kettle in one go through a side-feed tank with 3atm of nitrogen for 60min. Cooling to 70 deg.C, discharging, extracting unreacted maleic anhydride and maleic anhydride polymer with 70 deg.C 100g DMF for three times, and removing solvent by flash evaporation at 180 deg.C and vacuum degree of-0.085 MPa to obtain a solvent oil phase with softening point of 102.3 deg.C and acid value of 9.8mgKOH/g; gardner color number 0.7; the voc content was 0.13%. In comparison with example 1, 6.0g of triethylene glycol monoethyl ether cinnamate was introduced instead of 1.5g of α -methylstyrene, under the same conditions.
Example 7
300g of C9 hydrogenated petroleum resin HM100 with color number of 0.1 and aromatic hydrocarbon content of 4 percent is taken as a raw material (containing an antioxidant), 300g of solvent oil is added, the mixture is preheated to 80 ℃ until the petroleum resin is dissolved, the mixture is poured into a 1L reaction kettle while the mixture is hot, the reaction kettle is closed, stirring is started, the rotating speed is 300r/min, high-purity nitrogen with the pressure of 7atm is used for six times to remove oxygen, and then the temperature is raised to 160 ℃. 3.0g of maleic anhydride, 0.6g of initiator DCP and 9.0g of polyethylene glycol monoethyl ether laurate are dissolved in 6g of tetrahydrofuran and are pressed into a reaction kettle at one time through a side feeding tank by using 3atm nitrogen, and the reaction time is 60min. Cooling to 70 deg.C, discharging, extracting unreacted maleic anhydride and maleic anhydride polymer with 100g DMF at 70 deg.C for three times, and removing solvent by flash evaporation at 180 deg.C and vacuum degree of-0.085 MPa to obtain a solvent oil phase with softening point of 102.3 deg.C and acid value of 9.8mgKOH/g; gardner color number 1.1; the voc content was 0.16%.
In the same conditions as in example 1, 9.0g of polyethylene glycol monoethyl ether laurate was introduced instead of 1.5g of α -methylstyrene.
Example 8
300g of C9 hydrogenated petroleum resin HM100 with color number of 0.1 and aromatic hydrocarbon content of 4 percent is taken as a raw material (containing an antioxidant), 300g of solvent oil is added, the mixture is preheated to 80 ℃ until the petroleum resin is dissolved, the mixture is poured into a 1L reaction kettle while the mixture is hot, the reaction kettle is closed, stirring is started, the rotating speed is 300r/min, high-purity nitrogen with the pressure of 7atm is used for six times to remove oxygen, and then the temperature is raised to 160 ℃. 3.0g of maleic anhydride, 0.6g of initiator DCP and 3.0g of isopropyl cinnamate are dissolved in 6g of tetrahydrofuran, and the mixture is pressed into a reaction kettle at one time through a side feeding tank by using 3atm nitrogen for 30min. Cooling to 70 deg.C, discharging, extracting unreacted maleic anhydride and maleic anhydride polymer with 70 deg.C 100g DMF for three times, and removing solvent by flash evaporation at 180 deg.C and vacuum degree of-0.085 MPa to obtain a solvent oil phase with softening point of 102.5 deg.C and acid value of 9.5mgKOH/g; gardner color number 0.5; the voc content was 0.12%. Compared with the example 1, under the same conditions, the reaction time is shortened to 30min by introducing 3.0 parts of isopropyl cinnamate, and the acid value of the petroleum resin grafted and modified by maleic anhydride is obviously improved. Meanwhile, the cinnamate has a polar ester group, so that the compatibility with a polar material is improved.
Comparative example 1
Unmodified C9 hydrogenated petroleum resin HM1000 is used as tackifying resin, pressure sensitive adhesive is prepared according to the same proportion with the modified resin, and the performance of the pressure sensitive adhesive is tested.
Comparative example 2
Based on parts by weight, 100 parts of C9 hydrogenated petroleum resin with color number of 0.1 and aromatic hydrocarbon content of 4 percent is taken as a raw material (containing antioxidant), 1 part of maleic anhydride and 0.2 part of initiator DCP are dissolved in 2 parts of tetrahydrofuran and are uniformly mixed with the resin. Processing the petroleum resin, the initiator and the DCP which are uniformly mixed by using a double-screw extruder, wherein the temperatures of four zones of the extruder are respectively set to be 60, 150, 170 and 130 ℃, the retention time is 1-2min, so as to obtain the melt grafted petroleum resin, the softening point is 101.4 ℃, and the acid value is 1.7mgKOH/g; gardner color number 2.1; the voc content was 0.3%. The differences from example 1 are: the synthesis method is a double-screw melt grafting method. The experimental results show that the reaction time of the melt grafting method is short, so that the grafting efficiency is low, the acid value is obviously lower than that of the solution grafting method, and small molecules such as unreacted residual monomers, initiators and the like are difficult to remove, so that the voc content is obviously improved, and the odor is very large.
Comparative example 3
300g of C9 hydrogenated petroleum resin HM100 with color number of 0.1 and aromatic hydrocarbon content of 4 percent is taken as a raw material (containing an antioxidant), 300g of solvent oil is added, the mixture is preheated to 80 ℃ until the petroleum resin is dissolved, the mixture is poured into a 1L reaction kettle while the mixture is hot, the reaction kettle is closed, stirring is started, the rotating speed is 300r/min, high-purity nitrogen with the pressure of 7atm is used for six times to remove oxygen, and then the temperature is raised to 160 ℃. 3.0g of maleic anhydride and 0.6g of initiator DCP are dissolved in 6g of tetrahydrofuran and are pressed into the reaction kettle in one step by nitrogen of 3atm through a side feeding tank, and the reaction time is 60min. Cooling to 70 deg.C, discharging, extracting unreacted maleic anhydride and maleic anhydride polymer with 70 deg.C 200g water for three times, and removing solvent by flash evaporation at 180 deg.C and vacuum degree of-0.085 MPa to obtain a solvent oil phase with softening point of 101.5 deg.C and acid value of 3.7mgKOH/g; gardner color number 0.6; the voc content was 0.14%. The differences from example 1 are: no grafting activator alpha-methylstyrene was added and the extraction solvent used 200g of water instead of 100g of DMF during the extraction.
Comparative example 4
300g of C9 hydrogenated petroleum resin HM100 with color number of 0.1 and aromatic hydrocarbon content of 4% is used as a raw material (containing an antioxidant), 300g of solvent oil is added to preheat to 80 ℃ until the petroleum resin is dissolved, the mixture is poured into a 1L reaction kettle while the mixture is hot, the reaction kettle is closed, stirring is started, the rotating speed is 300r/min, high-purity nitrogen of 7atm is used for replacing for six times to remove oxygen, and then the temperature is raised to 160 ℃. 1.5g of maleic anhydride and 0.6g of initiator DCP are dissolved in 6g of tetrahydrofuran and are pressed into a reaction kettle in one step by a side feeding tank with 3atm nitrogen, and the reaction time is 60min. Cooling to 70 deg.C, discharging, extracting unreacted maleic anhydride and maleic anhydride polymer with 70 deg.C 200g water for three times, and removing solvent by flash evaporation at 180 deg.C and vacuum degree of-0.085 MPa to obtain a solvent oil phase with softening point of 101.8 deg.C and acid value of 1.9mgKOH/g; gardner color number 0.4, voc content 0.15%. The material amount of maleic anhydride is reduced, the acid value of the petroleum resin grafted and modified by the maleic anhydride is obviously reduced, the Gardner color number is also reduced, and the color of the resin is lighter. The differences from example 1 are: the amount of maleic anhydride was reduced from 3g to 1.5g, no grafting activator alpha-methylstyrene was added, and 200g of water was used as the extraction solvent instead of 100g of DMF during the extraction.
Comparative example 5
300g of C9 hydrogenated petroleum resin HM100 with color number of 0.1 and aromatic hydrocarbon content of 4 percent is taken as a raw material (containing an antioxidant), 300g of solvent oil is added, the mixture is preheated to 80 ℃ until the petroleum resin is dissolved, the mixture is poured into a 1L reaction kettle while the mixture is hot, the reaction kettle is closed, stirring is started, the rotating speed is 300r/min, high-purity nitrogen with the pressure of 7atm is used for six times to remove oxygen, and then the temperature is raised to 160 ℃. 9.0g of maleic anhydride and 0.6g of initiator DCP are dissolved in 6g of tetrahydrofuran and are pressed into the reaction kettle in one step by nitrogen of 3atm through a side feeding tank, and the reaction time is 60min. Cooling to 70 deg.C, discharging, extracting unreacted maleic anhydride and maleic anhydride polymer with 70 deg.C 200g water for three times, and removing solvent by flash evaporation at 180 deg.C and vacuum degree of-0.085 MPa to obtain a solution with softening point of 101.9 deg.C and acid value of 7.4mgKOH/g; gardner color number 1.1, voc content 0.14%. Under the same conditions as in example 1, the acid value of the petroleum resin graft-modified with maleic anhydride was increased by increasing the amount of maleic anhydride added, but the color was deepened to some extent, but the Gardner color number was still small. The differences from example 1 are: the amount of maleic anhydride was increased from 3g to 9.0g, no grafting activator alpha-methylstyrene was added, and the extraction solvent used was 200g of water instead of 100g of DMF during the extraction.
Comparative example 6
300g of C9 hydrogenated petroleum resin HM100 with color number of 0.1 and aromatic hydrocarbon content of 4 percent is taken as a raw material (containing an antioxidant), 300g of solvent oil is added, the mixture is preheated to 80 ℃ until the petroleum resin is dissolved, the mixture is poured into a 1L reaction kettle while the mixture is hot, the reaction kettle is closed, stirring is started, the rotating speed is 300r/min, high-purity nitrogen with the pressure of 7atm is used for six times to remove oxygen, and then the temperature is raised to 160 ℃. 3.0g of maleic anhydride and 1.2g of initiator DCP are dissolved in 6g of tetrahydrofuran and are pressed into the reaction kettle in one step by nitrogen of 3atm through a side feeding tank, and the reaction time is 60min. Cooling to 70 deg.C, discharging, extracting unreacted maleic anhydride and maleic anhydride polymer with 70 deg.C 200g water for three times, and removing solvent by flash evaporation at 180 deg.C and vacuum degree of-0.085 MPa to obtain a softening point of 101.5 deg.C and an acid value of 6.2mgKOH/g; gardner color number 1.7; the voc content was 0.15%. Compared with example 1, under the same conditions, the addition amount of the initiator DCP is doubled, the acid value of the petroleum resin modified by maleic anhydride grafting is obviously improved, but the color is obviously deepened, but the Gardner color number is still smaller. From the results, the acid value and color number of the modified petroleum resin are more sensitive to the initiator than maleic anhydride. The method also provides certain guiding significance for the formula and process design of the maleic anhydride grafted modified petroleum resin. The differences from example 1 are: the amount of initiator was increased from 0.6g to 1.2g without addition of the grafting activator alpha-methylstyrene and the extraction solvent used was 200g of water instead of 100g of DMF during the extraction.
Comparative example 7
300g of C9 hydrogenated petroleum resin HM100 with color number of 0.1 and aromatic hydrocarbon content of 4% is used as a raw material (containing an antioxidant), 300g of solvent oil is added to preheat to 80 ℃ until the petroleum resin is dissolved, the mixture is poured into a 1L reaction kettle while the mixture is hot, the reaction kettle is closed, stirring is started, the rotating speed is 300r/min, high-purity nitrogen of 7atm is used for replacing for six times to remove oxygen, and then the temperature is raised to 160 ℃. 3.0g of maleic anhydride and 0.6g of initiator DCP are dissolved in 6.0g of tetrahydrofuran and are put into a reaction kettle for four times by a miniature metering pump when the reaction time is 0, 15, 30 and 45min, and the total reaction time is 60min. Cooling to 70 deg.C, discharging, extracting unreacted maleic anhydride and maleic anhydride polymer with 70 deg.C 200g water for three times, and removing solvent by flash evaporation at 180 deg.C and vacuum degree of-0.085 MPa to obtain a solvent oil phase with softening point of 101.5 deg.C and acid value of 4.8mgKOH/g; gardner color number 0.4; the voc content was 0.16%. Compared with the example 1, under the same conditions, the acid value of the petroleum resin modified by maleic anhydride grafting can be improved by more than 20 percent and the color is slightly lighter when the initiator DCP and the maleic anhydride are added in batches. The differences from example 1 are: no grafting activator alpha-methylstyrene was added, the reaction material was pumped in four times and the extraction solvent used was 200g of water instead of 100g of DMF during the extraction.
Comparative example 8
300g of C9 hydrogenated petroleum resin HM100 with color number of 0.1 and aromatic hydrocarbon content of 4 percent is taken as a raw material (containing an antioxidant), 300g of trimethylbenzene is added and preheated to 80 ℃ until the petroleum resin is dissolved, the mixture is poured into a 1L reaction kettle while the mixture is hot, the reaction kettle is closed, stirring is started, the rotating speed is 300r/min, high-purity nitrogen with the pressure of 7atm is used for six times to remove oxygen, and then the temperature is raised to 160 ℃. 3.0g of maleic anhydride and 0.6g of initiator DCP are dissolved in 6g of tetrahydrofuran and are pressed into the reaction kettle in one step by nitrogen of 3atm through a side feeding tank, and the reaction time is 60min. Cooling to 70 deg.C, discharging, extracting unreacted maleic anhydride and maleic anhydride polymer with 70 deg.C 200g water for three times, and removing solvent by flash evaporation at 180 deg.C and vacuum degree of-0.085 MPa to obtain a solvent oil phase with softening point of 101.5 deg.C and acid value of 5.0mgKOH/g; gardner color number 0.5; the voc content was 0.14%. Compared with the example 1, under the same conditions, trimethylbenzene is used for replacing solvent oil, maleic anhydride is completely dissolved in the solvent, a grafting activator alpha-methyl styrene is not added, 200g of water is used for replacing 100g of DMF in the extraction solvent, the acid value of the petroleum resin grafted and modified by maleic anhydride is improved by more than 30%, and the color is not obviously changed.
Comparative example 9
300g of C9 hydrogenated petroleum resin HM100 with color number of 0.1 and aromatic hydrocarbon content of 4% is used as a raw material (containing an antioxidant), 300g of solvent oil is added to preheat to 80 ℃ until the petroleum resin is dissolved, the mixture is poured into a 1L reaction kettle while the mixture is hot, the reaction kettle is closed, stirring is started, the rotating speed is 300r/min, high-purity nitrogen of 7atm is used for replacing for six times to remove oxygen, and then the temperature is raised to 160 ℃. 3.0g of maleic anhydride and 0.6g of initiator DCP are dissolved in 6g of tetrahydrofuran and are pressed into the reaction kettle in one step by nitrogen of 3atm through a side feeding tank, and the reaction time is 60min. Cooling to 70 deg.C, discharging, extracting unreacted maleic anhydride and maleic anhydride polymer with 70 deg.C 200g DMF for three times, and removing solvent by flash evaporation at 180 deg.C and vacuum degree of-0.085 MPa to obtain a solution with softening point of 101.5 deg.C and acid value of 3.6mgKOH/g; gardner color number 0.6; the voc content is 0.10%. Compared with example 1, without the addition of the grafting activator α -methylstyrene, the amount of DMF was changed from 100g to 200g. The strong polar DMF is used for replacing water for extraction, so that most of impurities can be removed by one extraction, the voc content is reduced, and the smell is smaller.
Comparative example 10
300g of C9 hydrogenated petroleum resin HM100 with color number of 0.1 and aromatic hydrocarbon content of 4 percent is taken as a raw material (containing an antioxidant), 300g of solvent oil is added, the mixture is preheated to 80 ℃ until the petroleum resin is dissolved, the mixture is poured into a 1L reaction kettle while the mixture is hot, the reaction kettle is closed, stirring is started, the rotating speed is 300r/min, high-purity nitrogen with the pressure of 7atm is used for six times to remove oxygen, and then the temperature is raised to 180 ℃. 3.0g of maleic anhydride and 0.6g of initiator DCP were dissolved in 6g of tetrahydrofuran and were once forced into the autoclave through a side-feed tank with 3atm of nitrogen for 60min. Cooling to 70 deg.C, discharging, extracting unreacted maleic anhydride and maleic anhydride polymer with 70 deg.C 200g water for three times, and removing solvent by flash evaporation at 180 deg.C and vacuum degree of-0.085 MPa to obtain a solvent oil phase with softening point of 101.8 deg.C and acid value of 4.0mgKOH/g; gardner color number 1.0; the voc content was 0.16%. Compared with the example 1, the reaction temperature is increased from 160 ℃ to 180 ℃ without adding the grafting activator alpha-methyl styrene, 200g of water is used for replacing 100g of DMF in the extraction solvent, and under the same conditions, the reaction temperature is increased, the acid value of the petroleum resin modified by maleic anhydride grafting is slightly increased, but the color number is also increased, so that the color is darkened. It is worth mentioning that different initiators are present at different preferred temperatures and that the reaction time should be matched to the half-life of the initiator. In terms of trends, the higher the temperature, the darker the color of the graft-modified petroleum resin, and may be related to the thermal stability of the petroleum resin itself.
Comparative example 11
300g of C9 hydrogenated petroleum resin HM100 with color number of 0.1 and aromatic hydrocarbon content of 4 percent is taken as a raw material (containing an antioxidant), 300g of solvent oil is added, the mixture is preheated to 80 ℃ until the petroleum resin is dissolved, the mixture is poured into a 1L reaction kettle while the mixture is hot, the reaction kettle is closed, stirring is started, the rotating speed is 300r/min, high-purity nitrogen with the pressure of 7atm is used for six times to remove oxygen, and then the temperature is raised to 160 ℃. 3.0g of maleic anhydride and 0.6g of initiator DCP were dissolved in 6g of tetrahydrofuran and were once forced into the autoclave through a side-feed tank with 3atm of nitrogen for 30min. Cooling to 70 deg.C, discharging, extracting unreacted maleic anhydride and maleic anhydride polymer with 70 deg.C 200g water for three times, and removing solvent by flash evaporation at 180 deg.C and vacuum degree of-0.085 MPa to obtain a solution with softening point of 101.5 deg.C and acid value of 1.8mgKOH/g; gardner color number 0.4; the voc content was 0.15%. Compared with example 1, without the addition of the grafting activator alpha-methylstyrene, the reaction time was reduced from 60min to 30min, and 200g of water was used as the extraction solvent instead of 100g of DMF during the extraction. The results show that the grafting yield of the product is reduced and the acid value is reduced. The reaction time has a significant effect on the acid value within a certain range, but too long a time tends to result in a deepening of the color.
Map information:
FIG. 1 shows the IR spectra after grafting of comparative example 1 (curve 1) and example 2 (curve 2) without grafting.
FIG. 2 is an infrared spectrum of the resins prepared in example 1 (curve A), example 2 (curve B) and comparative example 1 (curve C) with the ordinate being the infrared absorption Abs of the radicals.
FIG. 3 is a partial magnified view of the IR spectra of the resins prepared in example 1 (curve A), example 2 (curve B) and comparative example 1 (curve C). Wave number of 1786cm -1 The carbonyl absorption peak is grafted with maleic anhydride groups; wave number 1714cm -1 The peak is the carbonyl absorption peak after isopropyl cinnamate grafting. Example 2 comparison with example 1, curve B shows 1786cm after maleic anhydride grafting -1 The absorption peak is stronger and is 1714cm at wave number -1 The characteristic absorption peak of the carbonyl group appears, which proves that the isopropyl cinnamate is grafted to the C9 petroleum resin and the grafting rate of the maleic anhydride is improved.
The synthetic scheme and performance data for the modified C9 hydrogenated petroleum resin are shown in table 1.
TABLE 1
Note: comparative example 7, the anhydride and initiator used were added in four portions; example 1, the activator used was alpha-methylstyrene; example 2 the activator used was isopropyl cinnamate; example 3 the activator used was cinnamyl cinnamate; example 4, the activator used was stearyl cinnamate; example 5 the activator used was triethylene glycol monoethyl ether cinnamate; example 6 the activator used was triethylene glycol monoethyl ether cinnamate; example 7 the activator used was polyethylene glycol monoethyl ether laurate. Example 8, reaction time 30min. A list of sources of materials used in the examples is shown in Table 2.
TABLE 2
Octadecyl cinnamate, triethylene glycol monoethyl ether cinnamate and polyethylene glycol monoethyl ether laurate were prepared by reacting cinnamoyl chloride with the corresponding octadecyl alcohol, triethylene glycol monoethyl ether and polyethylene glycol (PEG-400) monoethyl ether in pyridine.
The classical pressure-sensitive adhesive formula is 50.0wt% of petroleum resin in parts by weight; thermoplastic elastomer SIS 30.0wt%; naphthenic oil 19.5wt%; 0.5 percent of antioxidant. Therefore, the performance of the acid modified C9 hydrogenated petroleum resin is evaluated by replacing the C9 hydrogenated petroleum resin, and the formula comprises the following components in parts by weight:
acid-modified C9 hydrogenated Petroleum resin HM1000 wt%;
thermoplastic elastomer SIS, designation YH1126 30%. China petrochemical barron petrochemical company.
Naphthenic oil KN4010, 19.5%, xinjiang Clamayi petrochemical company.
5363% of an antioxidant 1010,0.5%, basf, germany.
The preparation method of the pressure-sensitive adhesive comprises the following steps: weighing 30 weight percent of SIS elastomer YH1126 by using a beaker, adding 19.5 weight percent of naphthenic oil KN4010, adding 0.5 percent of antioxidant 1010, stirring by using a glass rod, heating to 160 ℃, and continuously stirring for 15min until the polymer is completely dissolved; adding 50 weight percent of acid modified hydrogenated petroleum resin HM1000, and continuously stirring for 15min at 160 ℃ until a uniform and stable solution without blocky solids is obtained; and (3) placing the glue solution into a drying oven at 160 ℃ for standing for 30min to eliminate bubbles, wherein the glue solution can be directly coated. The film was coated between release paper and a polyethylene terephthalate (PET) film in a dried thickness of 30 μm, dried at 120 ℃ for 3min to obtain a three-layer release paper/pressure-sensitive adhesive/PET film having an upper layer of release paper, a middle layer of pressure-sensitive adhesive and a PET film as a liner, and cut into a test piece A one inch wide.
Pressure-sensitive adhesives were prepared as comparative example 1, comparative examples 2 to 11 and examples 1 to 8 using the resins in synthetic comparative example 1, synthetic comparative examples 2 to 11 and examples 1 to 8 in Table 1.1, respectively, according to the procedure described above.
The release paper of the test article A was peeled at a temperature of 23. + -.1 ℃ and a relative humidity of 50. + -.5% to obtain a PET/pressure-sensitive adhesive of a two-layer material. And (3) closely adhering the pressure-sensitive adhesive surface of the PET/pressure-sensitive adhesive double-layer material with a standard stainless steel plate to obtain the PET/pressure-sensitive adhesive/stainless steel plate three-layer material. Then, the pressure-sensitive adhesive and the stainless steel plate were tightly adhered by rolling three times at 0.25MPa and 300 mm/min to prepare a peel strength test standard.
The peel strength was tested according to GBT 2792-2014, under the following test conditions: temperature: (23 +/-1) DEG C, relative humidity (50 +/-5)%, glass angle, 180 DEG; peel test tensile rate: 300 mm/min. The Universal testing machine manufacturer, shimadzu corporation, japan.
The release paper of the test article A was peeled at a temperature of 23. + -.1 ℃ and a relative humidity of 50. + -.5% to obtain a PET/pressure-sensitive adhesive of a two-layer material. And lightly attaching the pressure-sensitive adhesive surface of the PET/pressure-sensitive adhesive double-layer material to a standard stainless steel plate to prepare the Loop tack test standard sample.
The Loop tack test method for the initial viscosity test of the pressure sensitive adhesive is characterized by comprising the following steps: (23. + -. 1). Degree.C. The apparatus used in the Loop tack was a LT-1000 Loop type tape tack tester, manufactured by ChemInstructions, USA.
And (3) peeling off the release paper of the test body A at the temperature of 23 +/-1) DEG C and the relative humidity of 50 +/-5% to obtain the double-layer material PET/pressure-sensitive adhesive, namely the PET/pressure-sensitive adhesive can be used for the holding power test of the pressure-sensitive adhesive. Pressure sensitive adhesive tack test standard: GBT4851-2014 assay, test temperature: at 40 ℃. Sacheng apparatus viscometry tester, model CZY-8S, weight (1000 + -5) g.
The thickness of the release paper used in the invention is 50 μm, and the manufacturer is Dongxin composite material Co.
The thickness of the PET film used in the invention is 50 μm, and the manufacturer is Ningbo Yang science and technology Co.
The Coater used in the present invention is a Hot Melt Lab Coater/HLCL-1000 Coater from ChemInstructions, USA.
Pressure sensitive adhesives were prepared according to the above formulation for the acid modified light colored good, low odor C9 hydrogenated petroleum resin and ring tack, permanent tack, and peel strength tests were performed according to the above test methods and the results are shown in table 3.
TABLE 3
As can be seen from Table 3, as the acid value increases, the permanent adhesion and the peel strength increase significantly, because more acid anhydride or carboxyl groups can form chemical bonds with the metal surface, increasing the adhesion effect.
Compared with the comparative examples 1, 2 and 3, the initial adhesion of the hot melt adhesive prepared from the graft-modified C9 hydrogenated petroleum resin is obviously improved, and the peel strength is positively correlated with the acid value.
From the comparison between comparative example 3 and examples 1 to 8, it can be found that the introduction of preferred grafting activators such as α -methylstyrene, isopropyl cinnamate, octadecyl 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 playing an important role in improving the tack strength and peel strength of the pressure-sensitive adhesive.
In combination with comparative example 3 and comparative example 11, from the comparison of example 2 and example 8, it can be seen that the graft reaction time was reduced from 60min to 30min after introduction of the graft activator isopropyl cinnamate, the residence time of the resin at high temperature was reduced, and the color number was reduced. Other performance indexes have small change, and the production efficiency can be improved while the product quality can be ensured in industrial production.
It can be seen from examples 4 and 7 that the introduction of the long-chain alkyl group improves the fluidity of the modified C9 hydrogenated petroleum resin and significantly improves the annular initial adhesion of the pressure sensitive adhesive.
The introduction of polar ester monomers, particularly cinnamate compounds containing a plurality of ether bonds, also obviously increases the polarity of the resin, thereby improving the wettability with polar materials and the constant viscosity of the pressure-sensitive adhesive.
Compared with the example 3, the comparative example 5 and the comparative example 1, the initial adhesion is improved by 34 percent and 25 percent respectively, the peeling strength is improved by 25 percent and 14.4 respectively under the condition of basically keeping the color number and the odor not increased, but the adhesive holding force is not obviously improved. The introduction of acid anhydride groups and polar ester groups which can participate in chemical reaction, particularly the introduction of ester groups containing long-chain alkyl groups, can play a role in remarkably improving initial adhesion and peeling strength, and the two groups complement each other to play a certain synergistic effect.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects: and extracting small molecular substances influencing smell and color by using a strong polar solvent, and reducing the voc content, thereby preparing the acid modified C9 hydrogenated petroleum resin with small smell. In the grafting reaction process, the grafting activator is introduced, so that the grafting efficiency and the grafting rate of the acidifier can be remarkably improved, the using amount of the initiator can be reduced or the reaction time can be reduced, and the grafting activator plays an important role in reducing the color of the acid-modified C9 hydrogenated petroleum resin and improving the production efficiency. By applying the technical scheme of the invention, the specific polar grafting activating agent is added in the grafting reaction process to promote the grafting reaction, and the grafting efficiency of unsaturated anhydride and/or unsaturated acid and the acid value of the modified C9 hydrogenated petroleum resin are effectively improved, so that the permanent adhesion and the peel strength when the modified C9 hydrogenated petroleum resin is used as a pressure-sensitive adhesive in the follow-up process can be greatly improved. On the other hand, the cinnamate activators contain polar groups, and the polarity of the modified C9 hydrogenated petroleum resin can be improved by taking the cinnamate activators as grafting activators, so that the wettability and compatibility of the modified C9 hydrogenated petroleum resin and polar materials can be improved. Meanwhile, the polar extraction of the strong polar solvent can remove small molecular substances (such as initiator residues, unreacted raw materials, polymers and the like) which influence the smell and the color in a grafting product system, so that the prepared modified C9 hydrogenated petroleum resin also has the characteristics of light color number, low voc content and the like. In conclusion, 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 widen the application of the C9 hydrogenated petroleum resin.
It should be noted that the terms "first," "second," and the like in the description and in the claims of the present application are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. 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 or illustrated herein.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in 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.
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| CN202211707389.4A CN115975132A (en) | 2022-12-27 | 2022-12-27 | Modified C9 hydrogenated petroleum resin, preparation method and application thereof |
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| CN202211707389.4A CN115975132A (en) | 2022-12-27 | 2022-12-27 | Modified C9 hydrogenated petroleum resin, preparation method and application thereof |
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