Dicyclopentadiene hydrogenated petroleum resin, BOPP film and preparation method thereof

Abstract

The invention discloses a dicyclopentadiene hydrogenated petroleum resin, a BOPP film and a preparation method thereof, and belongs to the technical field of polymer materials. The preparation of the dicyclopentadiene hydrogenated petroleum resin comprises: dissolving dicyclopentadiene and perfluoropolyether monomers in an organic solvent and then subjecting the monomers to a thermal polymerization reaction to obtain a petroleum resin; subjecting the petroleum resin to a hydrogenation reaction with hydrogen in the presence of a catalyst to obtain the dicyclopentadiene hydrogenated petroleum resin. By introducing a perfluoro functional group into the hydrogenated petroleum resin, the compatibility of the hydrogenated petroleum resin with the polypropylene resin can be improved, and the processing and utilization performance can be improved; at the same time, the perfluoro functional group has the characteristics of low surface free energy, which can improve the hydrophobic and anti-adhesion effects of the film product, and the uniformly dispersed hydrogenated petroleum resin can also improve the glassy crystal phase region of the blended species, thereby improving the oxygen and water barrier properties of the film product. The BOPP film containing the above-mentioned dicyclopentadiene hydrogenated petroleum resin can have both good oxygen and water barrier properties.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, in particular to a dicyclopentadiene hydrogenated petroleum resin, a BOPP film and a preparation method thereof. Background Art

[0002] Biaxially Oriented Polypropylene (BOPP) is a plastic film made by a special process. BOPP film occupies an important position in the packaging material market with its advantages such as light weight, non-toxicity, odorlessness, moisture resistance, high mechanical strength, good dimensional stability, good printing performance and good transparency. The production process of BOPP film includes raw material preparation, melting, plasticizing extrusion, filtration, longitudinal stretching, transverse stretching, corona treatment, winding, aging treatment, slitting and finished products. BOPP film has high transparency, good gloss, good barrier properties, high impact strength and strong low temperature resistance. It is an ideal choice for packaging food, candy, cigarettes, tea, juice, milk, textiles, etc.

[0003] Although BOPP film has good general properties, in some applications, its barrier properties (referring to the film's ability to block gas, water vapor, light, etc.) still need to be further improved.

[0004] In view of this, the present invention is proposed. Summary of the invention

[0005] The object of the present invention is to provide a dicyclopentadiene hydrogenated petroleum resin, a BOPP film and a preparation method thereof, so as to solve or improve the above technical problems.

[0006] The present invention can be implemented like this:

[0007] In a first aspect, the present invention provides a method for preparing a dicyclopentadiene hydrogenated petroleum resin, comprising the following steps: dissolving dicyclopentadiene and perfluoropolyether monomers in an organic solvent and subjecting them to thermal polymerization reaction to obtain a petroleum resin;

[0008] The petroleum resin is subjected to a hydrogenation reaction with hydrogen in the presence of a catalyst to obtain dicyclopentadiene hydrogenated petroleum resin.

[0009] In an alternative embodiment, the perfluoropolyether monomer comprises perfluoropolyether acrylates or perfluoropolyether styrenes;

[0010] And / or, the organic solvent includes at least one of cyclohexane, benzene, toluene and xylene.

[0011] In an optional embodiment, the mass ratio of dicyclopentadiene to the organic solvent is 1:1.5 to 1:3, and the mass ratio of the perfluoropolyether monomer to dicyclopentadiene is 1:5 to 1:15.

[0012] In an optional embodiment, the temperature of the thermal polymerization reaction is 220° C. to 280° C., the pressure of the thermal polymerization reaction is 0.8 MPa to 2.0 MPa, and the time of the thermal polymerization reaction is 150 min to 300 min.

[0013] In an alternative embodiment, the catalyst is a nickel-based catalyst.

[0014] In an optional embodiment, the molar ratio of petroleum resin to hydrogen is 1:2 to 1:4, and the amount of the catalyst used is 0.5 wt% to 2.0 wt% of the petroleum resin.

[0015] In an optional embodiment, the hydrogenation reaction time is 180 min to 300 min, the hydrogenation reaction pressure is 4.0 MPa to 8.0 MPa, and the hydrogenation reaction temperature is 180° C. to 240° C.

[0016] In a second aspect, the present invention provides a dicyclopentadiene hydrogenated petroleum resin, which is prepared by the preparation method of any one of the aforementioned embodiments.

[0017] In a third aspect, the present invention provides a BOPP film with high barrier properties, wherein the raw materials for preparing the BOPP film include the dicyclopentadiene hydrogenated petroleum resin of the aforementioned embodiment.

[0018] In a fourth aspect, the present invention provides a method for preparing a BOPP film with high barrier properties as described in the aforementioned embodiment, comprising the following steps: preparing a masterbatch from dicyclopentadiene hydrogenated petroleum resin and homopolypropylene; mixing the masterbatch and homopolypropylene, followed by extrusion, sheet casting, biaxial stretching and post-treatment.

[0019] The beneficial effects of the present invention include:

[0020] By introducing perfluorinated functional groups into hydrogenated petroleum resin, the compatibility between hydrogenated petroleum resin and polypropylene resin can be improved, and the processing and utilization performance can be improved; at the same time, the perfluorinated functional groups have the characteristics of low surface free energy, which can improve the hydrophobic and anti-adhesion effects of film products. The uniformly dispersed hydrogenated petroleum resin can also improve the glassy crystal phase region of the blended species, thereby improving the oxygen and water barrier properties of the film products. The BOPP film containing the above-mentioned dicyclopentadiene hydrogenated petroleum resin can have better oxygen and water barrier properties. DETAILED DESCRIPTION

[0021] In order to make the purpose, technical scheme and advantages of the embodiments of the present invention clearer, the technical scheme in the embodiments of the present invention will be described clearly and completely below. If the specific conditions are not specified in the embodiments, they are carried out according to conventional conditions or conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments used is not specified, they are all conventional products that can be purchased commercially.

[0022] The dicyclopentadiene hydrogenated petroleum resin, BOPP film and preparation method thereof provided by the present invention are specifically described below.

[0023] The present invention provides a method for preparing dicyclopentadiene hydrogenated petroleum resin, comprising the following steps: dissolving dicyclopentadiene (DCPD) and perfluoropolyether monomer in an organic solvent and subjecting them to thermal polymerization reaction to obtain petroleum resin;

[0024] The petroleum resin is subjected to a hydrogenation reaction with hydrogen in the presence of a catalyst to obtain dicyclopentadiene hydrogenated petroleum resin.

[0025] The present invention creatively introduces perfluorinated functional groups into hydrogenated petroleum resin, thereby improving the compatibility of hydrogenated petroleum resin with polypropylene resin and improving processing and utilization performance; at the same time, the perfluorinated functional groups have low surface free energy characteristics, which can improve the hydrophobic and anti-adhesion effects of film products, and the uniformly dispersed hydrogenated petroleum resin can also improve the glassy crystal phase region of the blended species, which is beneficial to improving the oxygen and water barrier properties of the film products. However, the compatibility of traditional hydrogenated petroleum resin with polypropylene is poor, which limits the amount of hydrogenated petroleum resin added to polypropylene, resulting in poor barrier properties of the corresponding film products.

[0026] In some optional embodiments, the perfluoropolyether monomer may include perfluoropolyether acrylates or perfluoropolyether styrenes. In some typical embodiments, the perfluoropolyether monomer is perfluoropolyether styrenes.

[0027] The structural formula of the above-mentioned perfluoropolyether acrylate is as follows: ;

[0028] The structural formula of the above-mentioned perfluoropolyether styrene is as follows: ;

[0029] Where Rf=CF 3 CF 2 CF 2 O[CF(CF 3 )CF 2 O] n CF(CF 3 ), n=2~4.

[0030] In some optional embodiments, the organic solvent may illustratively include at least one of cyclohexane, benzene, toluene and xylene. In some typical embodiments, the organic solvent is toluene.

[0031] In some optional embodiments, the mass ratio of dicyclopentadiene to the organic solvent can be 1:1.5 to 1:3, such as 1:1.5, 1:2, 1:2.5 or 1:3, or other values ​​within the range of 1:1.5 to 1:3. In some typical embodiments, the mass ratio of dicyclopentadiene to the organic solvent is 1:2.

[0032] The mass ratio of the perfluoropolyether monomer to dicyclopentadiene can be 1:5 to 1:15, such as 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14 or 1:15, etc., or other values ​​within the range of 1:5 to 1:15. In some typical embodiments, the mass ratio of the perfluoropolyether monomer to dicyclopentadiene is 1:10.

[0033] If the mass ratio of perfluoropolyether monomer to dicyclopentadiene is less than 1:5 (such as 1:2), it is not conducive to the synthesis of the petroleum resin structure; if the mass ratio of perfluoropolyether monomer to dicyclopentadiene is greater than 1:15 (such as 1:18), the proportion of perfluoro groups is too small, and the effect of improving the hydrophobicity and anti-adhesion properties of the membrane products is not obvious.

[0034] In some optional embodiments, the temperature of the thermal polymerization reaction can be 220° C. to 280° C., such as 220° C., 225° C., 230° C., 235° C., 240° C., 245° C., 250° C., 255° C., 260° C., 265° C., 270° C., 275° C. or 280° C., etc., or other values ​​within the range of 220° C. to 280° C. In some more typical embodiments, the temperature of the thermal polymerization reaction is 240° C. to 260° C.

[0035] If the temperature of the thermal polymerization reaction is lower than 220°C, it is not conducive to the formation of a polymerization product with a target molecular weight; if the temperature of the thermal polymerization reaction is lower than 280°C, the color of the petroleum resin product will deepen and the appearance of the film after processing will also be affected.

[0036] In some optional embodiments, the pressure of the thermal polymerization reaction can be 0.8 MPa to 2.0 MPa, such as 0.8 MPa, 1.0 MPa, 1.2 MPa, 1.4 MPa, 1.6 MPa, 1.8 MPa or 2.0 MPa, etc., or other values ​​within the range of 0.8 MPa to 2.0 MPa. In some typical embodiments, the pressure of the thermal polymerization reaction is 1.0 MPa to 2.0 MPa.

[0037] In some optional embodiments, the thermal polymerization reaction time can be 150 min to 300 min, such as 150 min, 180 min, 200 min, 220 min, 250 min, 280 min or 300 min, etc., or other values ​​within the range of 150 min to 300 min. In some typical embodiments, the thermal polymerization reaction time is 180 min to 240 min.

[0038] In some optional embodiments, the catalyst is a nickel-based catalyst. For example, the average pore size of the nickel-based catalyst used in the present invention can be 5nm to 30nm (such as 5nm, 10nm, 15nm, 20nm, 25nm or 30nm, etc.), and the nickel content can be 40wt% to 85wt% (such as 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt%, 80wt% or 85wt%, etc.).

[0039] In some optional embodiments, the molar ratio of petroleum resin to hydrogen can be 1:2 to 1:4, such as 1:2, 1:2.5, 1:3, 1:3.5 or 1:4, etc., or other values ​​within the range of 1:2 to 1:4. In some typical embodiments, the molar ratio of petroleum resin to hydrogen is 1:3.

[0040] In some optional embodiments, the amount of the catalyst can be 0.5wt% to 2.0wt% of the petroleum resin, such as 0.5wt%, 1.0wt%, 1.5wt% or 2.0wt%, etc., or other values ​​within the range of 0.5wt% to 2.0wt%. In some more typical embodiments, the amount of the catalyst is 1.5wt% of the petroleum resin.

[0041] In some optional embodiments, the hydrogenation reaction time can be 180 min to 300 min, such as 180 min, 200 min, 220 min, 250 min, 280 min or 300 min, etc., or other values ​​within the range of 180 min to 300 min. In some typical embodiments, the hydrogenation reaction time is 240 min to 300 min.

[0042] In some optional embodiments, the pressure of the hydrogenation reaction can be 4.0MPa~8.0MPa, such as 4.0MPa, 4.5MPa, 5.0MPa, 5.5MPa, 6.0MPa, 6.5MPa, 7.0MPa, 7.5MPa or 8.0MPa, etc., or other values ​​within the range of 4.0MPa~8.0MPa. In some typical embodiments, the pressure of the hydrogenation reaction is 6.0MPa~8.0MPa.

[0043] In some optional embodiments, the temperature of the hydrogenation reaction can be 180°C to 240°C, such as 180°C, 185°C, 190°C, 195°C, 200°C, 205°C, 210°C, 215°C, 220°C, 225°C, 230°C, 235°C or 240°C, etc., or other values ​​within the range of 180°C to 240°C. In some typical embodiments, the temperature of the hydrogenation reaction is 210°C to 240°C.

[0044] Correspondingly, the present invention also provides a dicyclopentadiene hydrogenated petroleum resin, which is prepared by the above preparation method.

[0045] The dicyclopentadiene hydrogenated petroleum resin has good compatibility with polypropylene, and can make the dicyclopentadiene hydrogenated petroleum resin and polypropylene have better blending processing performance. The dicyclopentadiene hydrogenated petroleum resin is suitable for preparing biaxially oriented polypropylene film (BOPP film), and can make the biaxially oriented polypropylene film have higher barrier properties.

[0046] In addition, the present invention also provides a BOPP film with high barrier properties. The raw materials for preparing the BOPP film include the above-mentioned dicyclopentadiene hydrogenated petroleum resin. The BOPP film has better water vapor and oxygen barrier properties.

[0047] Correspondingly, the present invention also provides a method for preparing the above-mentioned BOPP film with high barrier properties, comprising the following steps: preparing a masterbatch from dicyclopentadiene hydrogenated petroleum resin and homopolypropylene; mixing the masterbatch and homopolypropylene, followed by extrusion, sheet casting, biaxial stretching and post-treatment.

[0048] It should be noted that the present invention does not elaborate on the specific preparation conditions of the BOPP film, and the relevant content can refer to the prior art, and no further elaboration or limitation will be made here.

[0049] The features and performance of the present invention are further described in detail below in conjunction with the embodiments.

[0050] Example 1

[0051] This embodiment provides a dicyclopentadiene hydrogenated petroleum resin, and the preparation method thereof is as follows:

[0052] S1: Dissolving dicyclopentadiene (DCPD) and perfluoropolyether monomers in an organic solvent and subjecting them to thermal polymerization to obtain petroleum resin;

[0053] The organic solvent is toluene; the perfluoropolyether monomer is a styrene monomer, and the structural formula of the perfluoropolyether monomer is: , Rf=CF 3 CF 2 CF 2O[CF(CF 3 )CF 2 O] n CF(CF 3 ), n = 2. The mass ratio of DCPD to toluene is 1:1.5; the mass ratio of perfluoropolyether monomer to DCPD is 1:10; the temperature of the thermal polymerization reaction is 240°C, the pressure of the thermal polymerization reaction is 1.0 MPa, and the time of the thermal polymerization reaction is 210 min.

[0054] S2: hydrogenating the petroleum resin with hydrogen in the presence of a catalyst to obtain dicyclopentadiene hydrogenated petroleum resin.

[0055] The catalyst is a nickel-based catalyst, specifically, the average pore size of the catalyst is 10 nm, the nickel content is 65 wt %. The molar ratio of petroleum resin to hydrogen is 1:3; the amount of the catalyst is 1.5 wt % of the petroleum resin; the hydrogenation reaction time is 300 min, the hydrogenation reaction pressure is 6.0 MPa, and the hydrogenation reaction temperature is 240°C.

[0056] Embodiments 2 to 7

[0057] The reaction raw materials used in Examples 2 to 7 are the same as those used in Example 1. The process conditions involved in steps S1 and S2 in each example are shown in Tables 1 and 2.

[0058] Table 1 Summary of reaction conditions for step S1

[0059]

[0060] Table 2 Summary of reaction conditions for step S2

[0061]

[0062] Example 8

[0063] The difference between this embodiment and embodiment 1 is that the perfluoropolyether monomer is a perfluoropolyether styrene monomer, and the structural formula of the perfluoropolyether monomer is: , Rf=CF 3 CF 2 CF 2 O[CF(CF 3 )CF 2 O] n CF(CF 3 ), n=3; the organic solvent is cyclohexane.

[0064] Example 9

[0065] The difference between this embodiment and embodiment 1 is that the perfluoropolyether monomer is a perfluoropolyether acrylate monomer, and the structural formula of the perfluoropolyether monomer is: , Rf=CF 3 CF 2 CF 2 O[CF(CF 3 )CF 2 O] n CF(CF 3 ), n=2.

[0066] Comparative Example 1

[0067] This comparative example provides a dicyclopentadiene hydrogenated petroleum resin, and its preparation method is as follows:

[0068] Dicyclopentadiene and toluene are dissolved in a mass ratio of 1:2, and reacted at 250°C and 1.0 MPa for 180 minutes to obtain dicyclopentadiene petroleum resin; then the dicyclopentadiene petroleum resin is mixed with hydrogen in a mass ratio of 1:3, and reacted at 240°C and 6.0 MPa for 300 minutes under the action of 1.5wt% of a catalyst to obtain dicyclopentadiene hydrogenated petroleum resin.

[0069] Comparative Example 2

[0070] The difference between this comparative example and Example 1 is that in S1, the mass ratio of the perfluoropolyether monomer to dicyclopentadiene is 1:18.

[0071] Comparative Example 3

[0072] The difference between this comparative example and Example 1 is that methacrylic acid is used instead of perfluoropolyether monomer.

[0073] Test example

[0074] ①. Taking Example 1 and Comparative Example 1 as examples, the dicyclopentadiene hydrogenated petroleum resin and homopolypropylene prepared in Comparative Example 1, and the dicyclopentadiene hydrogenated petroleum resin and homopolypropylene prepared in Example 1 were mixed in different proportions, and then formed into films using a flat plate vulcanizer (temperature of 200° C., pressure of 2.0 MPa), and then the cross-section of the film was observed under a scanning electron microscope. The results are shown in Table 3.

[0075] Table 3 Cross-section results

[0076]

[0077] It can be seen from Table 3 that compared with the dicyclopentadiene hydrogenated petroleum resin that has not been modified with a perfluoro group, the dicyclopentadiene hydrogenated petroleum resin grafted with perfluoropolyether has better compatibility with homopolypropylene. Specifically, at least when the amount of dicyclopentadiene hydrogenated petroleum resin reaches 20wt%, the dicyclopentadiene hydrogenated petroleum resin and homopolypropylene will not separate into phases after being mixed and pressed.

[0078] ②. The dicyclopentadiene hydrogenated petroleum resins obtained in the above Examples 1 to 9 and Comparative Examples 1 to 3 were respectively prepared into BOPP films in the following manners:

[0079] The dicyclopentadiene hydrogenated petroleum resin and homopolypropylene obtained in the above examples were mixed in a mass ratio of 1:1, and then extruded and granulated to form a masterbatch; the masterbatch was mixed with homopolypropylene in a mass ratio of 1:4, extruded at 230℃~250℃, and cast using a cold roller. After the casting, the film was preheated to 120℃ and stretched 5 times in the longitudinal direction; then preheated to 180℃ and stretched 8 times in the transverse direction to obtain a BOPP film.

[0080] Meanwhile, a control group was set up, in which homopolypropylene was directly extruded and granulated to form a masterbatch, and then a BOPP film without adding hydrogenated petroleum resin was obtained through the above steps.

[0081] The BOPP films prepared in each embodiment, comparative example and control group were subjected to performance tests, wherein Young's modulus was measured by a dynamic mechanical analyzer; haze was measured by a haze meter using the GB / T 2410-2008 method; gas permeability test: water vapor permeability was measured on a Permatran-w3 / 61 moisture permeator using the GB / T26253-2010 method; oxygen permeability was measured using an 8001 oxygen permeator according to the GB / T19789-2005 method.

[0082] The test results are shown in Table 4.

[0083] Table 4 Performance test results

[0084]

[0085] It can be seen from Table 4 that compared with the BOPP film without dicyclopentadiene hydrogenated petroleum resin (control group), the BOPP film with dicyclopentadiene hydrogenated petroleum resin has improved Young's modulus and gas permeability. This is because the hydrogenated petroleum resin has a higher glass transition temperature, which can increase the rubber-like amorphous phase stiffness of polypropylene and also reduce the gas permeability.

[0086] By comparing Examples 1 to 9 with Comparative Example 1, after dicyclopentadiene hydrogenated petroleum resin is grafted with perfluoro groups, the gas permeability of the BOPP film can be further reduced because the perfluoro groups have extremely low surface energy.

[0087] By comparing Example 1 with Comparative Example 2, even if the dicyclopentadiene hydrogenated petroleum resin is grafted with perfluoro groups, if the preparation conditions are not properly set, the oxygen barrier and water barrier properties of the BOPP film will be effectively improved.

[0088] By comparing Example 1 with Comparative Example 3, even if other monomer types that can also improve the compatibility of hydrogenated petroleum resin and polypropylene resin are used, the effect of improving the oxygen barrier and water barrier properties of BOPP film is far inferior to the effect obtained by the perfluoro group grafting specifically used in the present application.

[0089] In summary, the present invention creatively introduces perfluoro functional groups into hydrogenated petroleum resin, thereby improving the compatibility of hydrogenated petroleum resin with polypropylene resin and improving processing and utilization performance; at the same time, the perfluoro functional group has the characteristics of low surface free energy, which can improve the hydrophobic and anti-adhesion effects of the film product, and the uniformly dispersed hydrogenated petroleum resin can also increase the glassy crystalline phase region of the blended species, which is beneficial to improving the oxygen and water barrier properties of the film product.

[0090] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for preparing dicyclopentadiene hydrogenated petroleum resin, characterized in that: The following steps are involved: The dicyclopentadiene and perfluoropolyether monomers are dissolved in an organic solvent and then thermally polymerized to obtain a petroleum resin; The petroleum resin is subjected to a hydrogenation reaction with hydrogen in the presence of a catalyst to obtain a dicyclopentadiene hydrogenated petroleum resin; The perfluoropolyether monomer is a perfluoropolyether acrylate or a perfluoropolyether styrene; the structural formula of the perfluoropolyether acrylate is as follows: The structural formula of the perfluoropolyether styrene is as follows: ; Where, Rf = CF3CF2CF2O [CF (CF3) CF2O] n CF(CF3), n=2~4; The mass ratio of the dicyclopentadiene to the organic solvent is 1:1.5 to 1:3, and the mass ratio of the perfluoropolyether monomer to the dicyclopentadiene is 1:5 to 1:15; The dicyclopentadiene hydrogenated petroleum resin is used for preparing a BOPP film having both water vapor and oxygen barrier properties.

2. The preparation method according to claim 1, characterized in that: The organic solvent includes at least one of cyclohexane, benzene, toluene and xylene.

3. The preparation method according to any one of claims 1 to 2, characterized in that The temperature of the thermal polymerization reaction is 220° C. to 280° C., the pressure of the thermal polymerization reaction is 0.8 MPa to 2.0 MPa, and the time of the thermal polymerization reaction is 150 min to 300 min.

4. The preparation method according to claim 1, characterized in that: The catalyst is a nickel-based catalyst.

5. The preparation method according to claim 1, characterized in that: The molar ratio of the petroleum resin to the hydrogen is 1:2 to 1:4, and the amount of the catalyst is 0.5wt% to 2.0wt% of the petroleum resin.

6. The preparation method according to claim 4 or 5, characterized in that: The time of the hydrogenation reaction is 180 min to 300 min, the pressure of the hydrogenation reaction is 4.0 MPa to 8.0 MPa, and the temperature of the hydrogenation reaction is 180°C to 240°C.

7. A dicyclopentadiene hydrogenated petroleum resin, characterized in that: The method is prepared by any one of claims 1 to 6.

8. A BOPP film with high barrier properties, characterized in that: The raw material for preparing the BOPP film includes the dicyclopentadiene hydrogenated petroleum resin described in claim 7.

9. A method for preparing a BOPP film with high barrier properties as claimed in claim 8, characterized in that: The following steps are involved: The dicyclopentadiene hydrogenated petroleum resin and homopolypropylene are prepared into a masterbatch; the masterbatch and homopolypropylene are mixed, and then extruded, cast, biaxially stretched and post-treated.

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