WO2017003157A1 - Résine de pétrole hydrogénée, et son procédé de production et son utilisation - Google Patents

Résine de pétrole hydrogénée, et son procédé de production et son utilisation Download PDF

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Publication number
WO2017003157A1
WO2017003157A1 PCT/KR2016/006905 KR2016006905W WO2017003157A1 WO 2017003157 A1 WO2017003157 A1 WO 2017003157A1 KR 2016006905 W KR2016006905 W KR 2016006905W WO 2017003157 A1 WO2017003157 A1 WO 2017003157A1
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Prior art keywords
petroleum resin
hydrogenated petroleum
ppm
group
methyl
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Ceased
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PCT/KR2016/006905
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English (en)
Korean (ko)
Inventor
이상현
조민식
박준효
이중석
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Kolon Industries Inc
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Kolon Industries Inc
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Priority claimed from KR1020150191077A external-priority patent/KR20170003367A/ko
Priority claimed from KR1020160080204A external-priority patent/KR101805892B1/ko
Application filed by Kolon Industries Inc filed Critical Kolon Industries Inc
Priority to US15/740,641 priority Critical patent/US10647896B2/en
Priority to JP2017568070A priority patent/JP6827001B2/ja
Priority to CN201680049664.4A priority patent/CN107922552B/zh
Priority to EP16818190.7A priority patent/EP3318587A4/fr
Publication of WO2017003157A1 publication Critical patent/WO2017003157A1/fr
Anticipated expiration legal-status Critical
Priority to US16/839,383 priority patent/US11186754B2/en
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/04—Reduction, e.g. hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/14—Monomers containing five or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F240/00—Copolymers of hydrocarbons and mineral oils, e.g. petroleum resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L57/00—Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C08L57/02—Copolymers of mineral oil hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J157/00—Adhesives based on unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09J157/02—Copolymers of mineral oil hydrocarbons

Definitions

  • the present invention relates to a hydrogenated petroleum resin applicable to an adhesive, a method for producing the same, and a use thereof.
  • Hydrocarbon Resin is a typical tackifier, and is mainly used as a material that gives viscosity and adhesiveness to products such as adhesive tape, paint, ink, rubber, and tires.
  • the properties may be in a variety of forms from liquid of semi-fluid transparent to light yellow and transparent colorless water (Water White) as a liquid or solid thermoplastic at room temperature.
  • the production of petroleum resins is usually carried out using a catalyst (mainly AlCl 3 or BF 3 ), which is a diolefin C 5 or C 9 fraction, through polymerization, decatalysis, washing, and resin separation.
  • a catalyst mainly AlCl 3 or BF 3
  • the improvement of physical properties is attempted by other polymerization systems, such as radical polymerization.
  • U.S. Patent No. 5,410,004 discloses a petroleum resin prepared by thermal polymerization of dicyclopentadiene (DCPD) and an olefinic modifier in the presence of a strong acid catalyst.
  • DCPD dicyclopentadiene
  • these petroleum resins contain double bonds and unreacted substances in the molecular structure, and as they are vulnerable to heat or acid, transparency of the petroleum resin color during or after processing decreases, and a bad odor occurs. Accordingly, even when the hydrogenation reaction is performed to remove the double bond, various corrosion problems may occur during the hydrogenation reaction due to the strong acid catalyst. In addition, there is a problem of poor productivity due to low yield.
  • the petroleum resin can be used as it is after the polymerization, and recently used in the form of hydrogenated petroleum resin prepared by performing an additional hydrogenation process to improve the physical properties.
  • Hydrogenated petroleum resins are thermoplastic resins made from high-quality unsaturated hydrocarbons in high-temperature pyrolysis oils such as naphtha in petrochemical plants. They are excellent in heat and ultraviolet (UV) light and have properties that provide adhesion. Medical supplies, woodworking supplies, hygienic supplies are used in various ways.
  • US Patent No. 5,652,308 discloses a tackifying resin in which a part of C5 monomer is partially replaced with C3 monomer by copolymerizing DCPD prepared from C3 monomer propylene and C5 monomer using a metallocene catalyst. I've done it.
  • an expensive metallocene catalyst which is very vulnerable to oxygen and moisture must be used, and thus the process design is complicated and the manufacturing cost is high, and the yield is also very low, which is less than 30%. There was a problem that it is difficult to practically low.
  • the Applicant has conducted a multi-faceted study to produce a hydrogenated petroleum resin by performing a hydrogenation reaction after performing a thermal polymerization process rather than a complex catalytic polymerization, but comonomers in dicyclopentadiene as a raw material
  • the olefin monomers are used together, the adhesion and heat resistance of the hydrogenated petroleum resin finally obtained are improved and the odor is improved, and when applied to adhesives, the physical properties are also improved, thereby completing the present invention.
  • Another object of the present invention is to provide a hydrogenated petroleum resin produced by the above-described method is improved physical properties and odor.
  • Still another object of the present invention is to provide a use of the hydrogenated petroleum resin as an adhesive.
  • the present invention provides a hydrogenated petroleum resin comprising a repeating unit represented by the following formula (1) and (2):
  • R 1 is H or a methyl group
  • R 2 is an alkyl group of C1 to C18, 0 ⁇ m ⁇ 10 and 0 ⁇ n ⁇ 10)
  • the present invention comprises the steps of thermally polymerizing a dicyclopentadiene and a C3 to C20 olefin monomer to prepare a petroleum resin;
  • It provides a process for producing a hydrogenated petroleum resin comprising the step of performing a hydrogenation reaction by the hydrogenation catalyst of the petroleum resin.
  • the present invention also provides a use of the hydrogenated petroleum resin in the adhesive composition.
  • Hydrogenated petroleum resin manufacturing method can solve the supply-demand problem of the raw material by replacing the C3 olefins used as the raw material of the petroleum resin with olefins of 6 to 20 carbon atoms, the heat of polymerization rather than catalytic polymerization By using the polymerization step, the polymerization yield can be greatly improved.
  • the hydrogenated petroleum resin produced by the production method of the present invention has not been improved in the conventional petroleum resin to solve the problem that a characteristic unpleasant odor is generated, so that the odor is hardly generated.
  • the hydrogenated petroleum resin produced by the above production method has excellent odor, excellent adhesion performance, high softening point, transparent, low molecular weight, excellent color, compatibility with natural rubber or synthetic rubber, etc. It is excellent in that it can be usefully used as an adhesive in various fields, in particular, it can increase the competitiveness in the application to hygiene products.
  • FIG. 1 is a schematic diagram illustrating the NMR spectral analysis proposed in the present invention, (a) shows a peak area, and (b) shows a full width at half maximum.
  • Figure 2 is a flow chart showing a method for producing a hydrogenated petroleum resin proposed in the present invention.
  • Example 3 is a 1 H-NMR spectrum of the petroleum resin before hydrogenation of Example 1 according to the present invention.
  • Example 4 is a 1 H-NMR spectrum of the petroleum resin after hydrogenation of Example 1 according to the present invention.
  • Example 5 is a 1 H-NMR spectrum of the petroleum resin before hydrogenation of Example 5 according to the present invention.
  • Example 6 is a 1 H-NMR spectrum of the petroleum resin after hydrogenation of Example 5 according to the present invention.
  • Example 7 is a 1 H-NMR spectrum of the petroleum resin before hydrogenation of Example 7 according to the present invention.
  • Example 8 is a 1 H-NMR spectrum of the petroleum resin before hydrogenation of Example 8 according to the present invention.
  • Example 9 is a 1 H-NMR spectrum of the petroleum resin before hydrogenation of Example 9 according to the present invention.
  • the present invention proposes a petroleum resin of a new structure that can be applied to an adhesive or pressure-sensitive adhesive is improved odor.
  • the hydrogenated petroleum resin according to the present invention is prepared by thermal polymerization of dicyclopentadiene and an olefinic monomer and then produced through a hydrogenation reaction, and includes repeating units represented by the following Chemical Formulas 1 and 2:
  • R 1 is H or a methyl group
  • R 2 is an alkyl group of C1 to C18, 0 ⁇ m ⁇ 10 and 0 ⁇ n ⁇ 10)
  • R 1 is H
  • R 2 may be an alkyl group of C1 to C18.
  • the alkyl group may be a linear or branched alkyl group, preferably a linear alkyl group.
  • a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, or a tetradecyl group and among these, a C4 or more alkyl group, a butyl group and a pentyl group , Hexyl group, octyl group, nonyl group, decyl group, dodecyl group, or tetradecyl group is preferable.
  • Hydrogenated petroleum resin according to the present invention includes the repeating units of Chemical Formulas 1 and 2, but is in a saturated state without a double bond in the molecular structure, and these repeating units have a copolymerized form.
  • the form of the copolymer is expressed as described above for convenience, but is not particularly limited in the present invention, random copolymer, alternating copolymer (alternative copolymer), block copolymer (graft), graft copolymer (graft) Various forms such as copolymer and starblock copolymer are possible.
  • the repeating unit of Formula 1 is a repeating unit derived from dicyclopentadiene
  • Formula 2 is a repeating unit derived by a polymerization reaction of dicyclopentadiene and an olefin monomer which is a comonomer, and an alkyl group at the terminal It has a structure substituted with.
  • the odor of the petroleum resin is improved through the use of an olefin-derived alkyl group constituting the repeating unit of Formula 2.
  • the petroleum resin may contain 10 to 50 mol%, preferably 10 to 45 mol%, of the alkyl group derived from the olefin in the total petroleum resin.
  • the content of the alkyl group is less than the above range, it may be difficult to improve the adhesion performance and the odor improvement effect due to the copolymerization with the olefinic monomer. On the contrary, when the content exceeds the above range, the adhesion may be deteriorated.
  • repeating units of Formulas 1 and 2 are preferably present in a predetermined molar ratio, specifically, 40 to 90 mol% of repeating units of Formula 1 and 10 to 60 mol% of repeating units of Formula 2. If the repeating unit of Formula 2 is relatively small, it is not possible to secure an improvement effect such as odor and adhesion performance. On the contrary, when excessively used, the physical properties of the petroleum resin itself decrease, and thus it is appropriately used within the above range.
  • the structural analysis of the hydrogenated petroleum resin according to the present invention having the above structure may be performed through a 1 H-NMR analyzer (nuclear magnetic resonance, nuclear magnetic resonance spectroscopy), and the hydrogenated petroleum resin through the peak analysis obtained at this time It can be specified.
  • 1 H-NMR analysis is an analytical method that tells which atoms the hydrogen atoms in the compound are bound to, and which functional groups they contain. This method can be used for identification and identification of compounds, and can be used for quantitative analysis of mixtures and estimation of molecular structure, as well as for measuring binding state changes.
  • protons (H + ) having the same relationship in the molecule appear as one peak, and if they are in close proximity with other nuclei, they split and appear as multiplets.
  • the peak position of the chemical shift i.e., frequency interval, ppm
  • the chemical shift data can be used to extract information of what kind of protons are present in the molecule, what proportion each proton is present through the intensity, and which protons are adjacent to each other through coupling.
  • Hydrogenated petroleum resin proposed in the present invention has a repeating structure of Formulas (1) and (2), wherein the repeating unit of Formula (1) consists only of a ring structure derived from dicyclopentadiene, and Formula 2 is derived from an olefin together with the ring structure.
  • R 2 in Formula 2 may be confirmed to specify a hydrogenated petroleum resin.
  • the 1 H-NMR spectrum of the hydrogenated petroleum resin does not appear as a peak like the compound, but due to the presence of a large number of protons, they influence each other so that peaks exist in a predetermined area as shown in FIGS. 3 to 11.
  • the peaks associated with the repeating units of Formulas 1 and 2 have a large number of peaks up to 7.5 ppm.
  • the peak of 0.8-1.4 ppm is a proton peak derived from R ⁇ 2> , and the other is a proton peak derived from the ring structure of dicyclopentadiene.
  • the peak of the 1 H-NMR spectrum is related to the number of protons, and peak analysis between 0.8 and 1.4 ppm is very important to confirm that R 2 is bonded to the hydrogenated petroleum resin of the present invention.
  • the peak analysis is divided into a case where the peak area is used as a parameter and a case where the width of the peak is used as a parameter. That is, by analyzing the parameters related to the peak area and the width of the peak, quantitative analysis and qualitative analysis are possible, and the hydrogenation petroleum resin proposed in the present invention can be specified.
  • 1 is a schematic diagram for explaining 1 H-NMR spectral analysis proposed in the present invention, (a) shows the peak area, and (b) shows the definition of full width at half maximum.
  • the area of the a to b ppm peaks shown in the present invention of FIG. 1 (a) means the area of the corresponding area when cut in the vertical direction including the base line at a and b ppm points of the X-axis chemical shift. .
  • the width of the a 'ppm peak presented in the present invention of Figure 1 (b) is full width at half maximum (FWHM) is the peak including the base line at the a' point of the chemical shift of the X-axis It means the width at the half point (H / 2) of the height (H).
  • the hydrogenated petroleum resin of the present invention may be defined by a parameter of the peak area, where the peak area follows the definition as shown in FIG.
  • Alkyl group of R 2 in relation to olefin The peak appears in the range of 0.8 to 1.4 ppm, in which the peak is largely divided into two branches.
  • the peak at 0.8 to 1.0 ppm and the peak at 1.0 to 1.4 ppm are related to the amount of R 2 present, and the ratio of the peak at 0.8 to 1.0 ppm and the peak at 1.0 to 1.4 ppm is R 2. It is a peak which knows what kind of length of carbon number is, that is, the kind of olefin used.
  • the hydrogenated petroleum resin according to the present invention can estimate the content of R 2 in the total hydrogenated petroleum resin by measuring the area of the peak obtained after 1 H-NMR measurement.
  • the area can be easily derived from the NMR spectrometer.
  • the hydrogenated petroleum resin of the present invention has a peak area of 0.8 to 1.0 ppm relative to the peak area of 1.4 to 7.5 ppm in the NMR spectrum obtained after 1 H-NMR measurement, preferably 0.2 to 0.8, more preferably. It has a range of 0.5 to 0.7 below.
  • the area ratio is related to the content of R 2 and related to the effect to be obtained by substitution of an alkyl group. That is, when the area ratio is out of the above range, it is not possible to secure effects such as heat resistance improvement and odor improvement of the petroleum resin.
  • the hydrogenated petroleum resin of the present invention has a peak area of 1.0 to 1.4 ppm relative to the peak area of 1.4 to 7.5 ppm in the NMR spectrum obtained after 1 H-NMR measurement, preferably 0.5 to 0.8, more preferably It has a range of 0.6 to 0.7.
  • the area ratio is related to the type of R 2 and related to the effect to be obtained by substitution of an alkyl group. That is, when the area ratio is out of the above range, it is not possible to secure effects such as heat resistance improvement and odor improvement of the petroleum resin.
  • the NMR peak area parameter may exist to some extent an alkyl group (R 2 ) in the hydrogenated petroleum resin, and the type of the olefin monomer used may be predicted.
  • the area ratio of each peak may satisfy only one or more, and more preferably, all of them may be satisfied.
  • the hydrogenated petroleum resin of the present invention may be defined by a parameter of full width at half maxium (FWHM) of the peak, where the peak area follows the definition as shown in FIG.
  • FWHM full width at half maxium
  • a peak related to the R 2 is a peak at 1.0 ⁇ 1.4 ppm related to the peak, the type of R 2 in 0.8 ⁇ 1.0 ppm related to the amount of appears in 0.8 ⁇ 1.4 ppm, 2 R It is limited by the full width at half maximum parameter.
  • the full width at half maximum at 0.85 ppm in relation to the substitution degree of R 2 and the full width at half maximum at 1.20 ppm in relation to the number of carbon atoms of R 2 are preferably 0.1 ppm or less, preferably at 0.85 ppm. Below, it is 0.01-0.1 ppm, and the full width at half maximum of a 1.20 ppm peak is 0.4 ppm or less, Preferably it is 0.01-0.4 ppm.
  • the full width at half maximum parameter is a limited range in which adhesion performance and odor improvement can be achieved through the use of an olefinic monomer.
  • the hydrogenated petroleum resin according to the present invention may satisfy only one of the full width at half maximum at 0.85 ppm and 1.20 ppm, more preferably both.
  • the hydrogenated petroleum resin according to the present invention has a weight average molecular weight of 500 to 3,000 g / mol, a softening point of 90 to 150 ° C, and a color (APHA color) of 1 to 100. If the weight average molecular weight is less than 500g / mol may be the adhesive strength, if it exceeds 3000g / mol may be insufficient compatibility. If the softening point is less than 90 °C adhesive strength may fall, if it exceeds 150 °C is not preferable in terms of difficult application of the manufacturing process.
  • the weight average molecular weight is related to the field of application of hydrogenated petroleum resin, for example, is a range capable of fully exhibiting its function when applied to the field of adhesives presented in the following application part.
  • the molecular weight is less than the above range, a decrease in adhesion performance occurs, and on the contrary, the above-described range may be exceeded and compatibility with other resins may decrease.
  • the softening point refers to a temperature at which the softening point is deformed by heat to cause softening. If the softening point is too low when applied to the adhesive field, a problem may occur in that the petroleum resin itself is fused when the petroleum resin is stored, and vice versa. There may be a problem that the adhesiveness of the adhesive is lowered.
  • APHA color with respect to color is applied to measure the chromaticity of clear liquid and solid properties, it is usually expressed by subdividing in steps of 1 to 500, the number is correlated with the yellowness index (yellowness index) Has Hydrogenated petroleum resin of the present invention, the value of APHA is 1 to 100, when the value exceeds 100 exhibits an opaque characteristic or the color becomes turbid when mixed with other resins, the value of the product is reduced.
  • the compatibility shows how well the resin is miscible with other compositions.
  • the polyolefin rubber and the wax are mixed at a constant ratio, heated to become transparent, and cooled, while the resin composition is clouded at a point where the resin composition becomes cloudy. Compatibility was measured by cloud point. That is, the compatibility means that the room temperature to 150 °C means that the hydrogenated petroleum resin and other resin of the present invention can be mixed well at room temperature to 150 °C.
  • Hydrogenated petroleum resin comprises the steps of preparing a petroleum resin through a thermal polymerization reaction of dicyclopentadiene and olefins of C3 ⁇ C20;
  • the petroleum resin is prepared by performing a hydrogenation reaction with a hydrogenation catalyst to prepare a hydrogenated petroleum resin (see FIG. 2).
  • a petroleum resin is prepared by thermally polymerizing a C3 to C20 olefin monomer with dicyclopentadiene and a comonomer.
  • Olefin monomers used as comonomers include olefin compounds up to C20, including C3 olefins, which have conventionally been used as main raw materials for petroleum resins.
  • the olefinic monomer may be a linear or branched alpha olefinic monomer.
  • alpha olefin monomers in particular, when linear alpha olefins are used, are more flexible than branched alpha olefins, and have excellent fluidity and structural penetration. Thus, when used as an adhesive or an adhesive, a high wettability to the substrate can be secured to ensure high adhesion. have.
  • the alpha olefin monomer may be used as one type or a mixture of two or more kinds of the above-mentioned monomers, and is not particularly limited in the present invention.
  • Available olefinic monomers include ethylene (or ethene), propylene (or propene), 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1 Linear alpha-olefins such as dodecene, 1-tetradecene, 1-hexadecene and 1-aitocene, isobutylene, 3-methyl-1butene, 2-methyl-1-butene, 3-methyl-1- Butene, 4-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 5-methyl-1-hexene, dimethyl pentene, diethyl hexene, and the like.
  • Branched alpha-olefins, mixtures thereof and the like can be used alone or in combination, more preferably linear alpha olefins, most preferably 1-hexene, 1-heptene, 1-octene in the liquid state , 1-decene, dodecene and the like are used.
  • the polymerization of the dicyclopentadiene and the olefinic monomer is performed through thermal polymerization, not catalytic polymerization.
  • the dicyclopentadiene and the olefinic monomers When a certain level of heat is applied to the dicyclopentadiene and the olefinic monomers, they form radicals themselves, thereby causing an initiation reaction, and producing a petroleum resin through a continuous polymerization reaction. Since the thermal polymerization does not use an initiator, it is possible to solve the problem of increased cost and purity of the petroleum resin.
  • the molar ratio of the reactant during the thermal polymerization of the dicyclopentadiene and the olefin monomer is used in a molar ratio of 1: 0.2 to 1: 0.5, preferably 1: 0.25 to 1: 0.45 for the dicyclopentadiene and the olefin monomer. .
  • the molar ratio is related to the physical properties of the finally obtained hydrogenated petroleum resin, and if it is less than the above range, it is difficult to produce a hydrogenated petroleum resin having a desired level of physical property by using too few olefinic monomers. Since the content of the cyclopentadiene is relatively reduced to decrease the physical properties of the final hydrogenated petroleum resin, it is appropriately adjusted within the above range.
  • the thermal polymerization is not particularly limited in the present invention, and bulk polymerization and solution polymerization methods may be used. Preferably solution polymerization can be used.
  • dicyclopentadiene is dissolved in a solvent to prepare a dicyclopentadiene solution, and an olefin monomer is added to the obtained dicyclopentadiene solution. After the thermal polymerization is carried out.
  • the solvent may be any solvent as long as it can sufficiently dissolve the dicyclopentadiene as described above and is not limited in the present invention.
  • toluene, methylene chloride, hexane, xylene, trichloro benzene, alkylbenzene, acetonitrile, dimethylformamide, N-methylpyrrolidone, dimethylacetamide, dimethylsulfoxide, gamma-butyrolactone, furfural , Acetone and a mixed solvent thereof may be selected.
  • the content of the solvent may be so long as it can dissolve the dicyclopentadiene sufficiently.
  • the solvent is used in the range of 2 to 10 moles with respect to 1 mole of the dicyclopentadiene.
  • the thermal polymerization is carried out at a temperature at which the initiation and polymerization of the dicyclopentadiene and the olefinic monomer can occur sufficiently, and the temperature can be changed according to the type of the dicyclopentadiene and the olefinic monomer.
  • the reaction time is performed for 0.5 to 4 hours, preferably 1 to 2 hours. If the thermal polymerization is performed at 200 ° C. or less than 0.5 hours, the yield may be low, and gel may be formed when thermal polymerization is performed at 320 ° C. or more than 4 hours.
  • the temperature is directly related to the initiation and polymerization reaction, the initiation does not occur at a temperature below the above range, on the contrary, the decomposition of the dicyclopentadiene or olefin monomers or the formation of gels at the temperature above the above range does not occur. Occurs, and polymerization rate control is not easy.
  • reaction time is related to the yield, and if it is less than the above time, the yield may be low. On the contrary, even if the reaction is carried out for a long time, there is no large increase in yield, so it is uneconomical, and therefore it is appropriately used in the above range.
  • the present invention may solve the problem of difficult supply of raw materials of C5 olefins, which were used as main raw materials in conventional petroleum resins by thermal polymerization of dicyclopentadiene and olefinic monomers, and odor which has not been solved in conventional petroleum resins. Can solve the problem.
  • the catalyst removal process which is an essential step in the cationic catalyst process, which is a conventional petroleum resin manufacturing method, may not be required, and the yield may be greatly improved to 90% or more. desirable.
  • a hydrogenation catalyst is added to the petroleum resin prepared above and a hydrogenation reaction is performed to produce a hydrogenated petroleum resin.
  • Hydrogenation is a reaction in which hydrogen is added to a double bond in an unsaturated state to form a single bond, and a hydrogenated petroleum resin in which all double bonds are disappeared through a hydrogenation reaction to petroleum resin is produced.
  • the hydrogenation reaction is carried out by the addition of a hydrogenation catalyst and involves a high exothermic process, which makes the temperature control requirement difficult and maintains high pressure.
  • the hydrogenation reaction is carried out at 150 to 300 °C under a pressure of 50 to 150 bar. If the temperature and pressure are less than the above range, the hydrogenation reaction may not be sufficiently performed. On the contrary, if the temperature and the pressure exceed the above range, the molecular structure may be destroyed by the severe reaction conditions, and thus, appropriately controlled within the above range.
  • the hydrogenation catalyst used at this time is not specifically limited in this invention, Any known hydrogenation catalyst can be used.
  • the hydrogenation catalyst may be one selected from the group consisting of Ni, Fe, Cu, Co, Mo, Pd, Rh, Pt, Nb, Au, Rd, Raney Ni, and combinations thereof. Use Pd.
  • the hydrogenation catalyst is used in a molar ratio of 0.001 to 0.5, preferably 0.05 to 0.2, per mole of dicyclopentadiene. If less than 0.001 mole is used per 1 mole of dicyclopentadiene, the reactivity may be insufficient, and if it exceeds 0.5 mole, there is a disadvantage that it is not economical to use a large amount of catalyst.
  • the production method of hydrogenated petroleum resin according to the present invention can be produced with a high yield of hydrogenated petroleum resin through thermal polymerization, can simplify the process and reduce the cost and can be easily applied to the commercialization process.
  • the manufacturing method according to the present invention described above can produce a petroleum resin having a significantly improved odor with a high yield of 90% or more.
  • the petroleum resin prepared in the present invention can impart point and adhesive performance to hot melt adhesives, pressure-sensitive adhesives, inks, paints, road marking paints, and the like, and is blended with various resins such as natural rubber and synthetic rubber to form an adhesive. It can be usefully used.
  • the present invention is a petroleum resin comprising a repeating unit represented by the formula 1 and the repeating unit represented by the formula (2); Styrenic block copolymers such as styrene-isoprene block copolymer, styrene-isoprene-styrene block copolymer, styrene-butadiene block copolymer, styrene-butadiene-styrene block copolymer, polyethylene, polypropylene, At least one polymer selected from ethylene based poly olefin block copolymers such as ethylene vinyl acetate and propylene-ethylene copolymers; And an adhesive selected from the group consisting of synthetic waxes such as paraffin wax, microstalin wax, animal natural waxes, vegetable natural waxes, aromatic oils, naphthenic oils and paraffinic oils.
  • Styrenic block copolymers such as styrene-isoprene block copolymer
  • the softening point of the adhesive prepared from the adhesive composition is 50 to 150 °C, the melt viscosity is characterized in that 300 cps to 10,000 cps at 160 °C, 200 cps to 8,000 cps at 180 °C.
  • the softening point of the adhesive is less than 50 °C may be inferior to the adhesive force, if it exceeds 150 °C in terms of difficulty in the application of the manufacturing process is not preferable.
  • melt viscosity may be inferior in workability when exceeding 10,000 cps at 160 ° C, may be inferior in adhesive strength when less than 300 cps, and may be inferior in processability when it exceeds 8,000 cps at 180 ° C, and may be inferior in adhesiveness below 200 cps.
  • the adhesive prepared from the adhesive composition may be used as a hot melt adhesive (HMA) or a pressure sensitive adhesive (HMPSA).
  • HMA hot melt adhesive
  • HMPSA pressure sensitive adhesive
  • Hot melt adhesives have excellent properties as adhesives with compatibility of 100 °C or less, Hardness 30 to 90 °C, Open time 5 seconds to 30 seconds, Set time 0.1 seconds to 5 seconds. It can be seen that.
  • the ball tack method is 40 cm or less in the initial stage, 40 cm or less after aging, and is 500 gf / in or more in the peel strength method, 500 gf / in or more after the aging, and 30 in the holding power method. min or more, 30 min or more after aging, the initial 40 °C or more, 40 °C or more after aging in the SAFT method, it can be seen that it has excellent physical properties as a pressure-sensitive adhesive.
  • the adhesive according to the present invention is a hydrogenated petroleum resin which is free of double bonds by hydrogenation and is produced by thermal polymerization, so that unreacted raw materials, solvents and low molecular weight oligomers do not occur. Unpleasant smell (odor) is improved.
  • Such adhesives can be preferably used in all fields requiring the use of adhesives, especially hot melt pressure-sensitive adhesives or adhesives for hygiene products in contact with the human body such as diapers, sanitary napkins and adult diapers.
  • the petroleum resin before hydrogenation and the petroleum resin after hydrogenation were polymerized above was confirmed by measuring by using a nuclear magnetic resonance spectrometer (500 NMR of Bruke, 14.1 telsa), and the results are shown in FIGS. 3 and 4.
  • the 1 H-NMR spectrum result confirming the structure of the petroleum resin before hydrogenation is a peak indicating a methyl group (-CH 3 ) derived from 1-hexene between 0.85 and 0.95 ppm in the 1 H-NMR measurement as shown in FIG. 3. It can be seen that the peak increases, and at the same time, the peak indicating the ⁇ -CH 2- > chain of 1-hexene between 1.20 and 1.30 ppm increases, indicating that DCPD and 1-hexene are copolymerized.
  • the 1 H-NMR spectrum results confirming the structure of the petroleum resin after hydrogenation are as shown in Fig. 4, which shows peaks representing 1-hexene methyl groups (-CH 3 ) between 0.85 and 0.95 ppm in the 1 H-NMR measurement. Peak) is vaporized, and at the same time, peaks indicating ⁇ -CH 2- > chains of 1-hexene between 1.20 and 1.30 ppm increase, indicating that DCPD and 1-hexene are copolymerized resins, and at the same time 4.9 to 6.5 ppm It can be seen that the hydrogenation is completed by confirming that the double bond peak between is completely removed.
  • the peak between 0.85 and 0.95 ppm is the methyl group of the olefin
  • the peak between 1.20 and 1.30 ppm is the peak of the ⁇ -CH 2- > chain of the olefin and is between 4.9 and 6.5 ppm.
  • the peak is a peak of a double bond of dicyclopentadiene, and as shown in the results of FIGS. 3 and 4, the value of each peak is compared to determine whether DCPD and olefin (Olefin) are copolymerized and whether the hydrogenation reaction proceeds. You can check it.
  • Petroleum resins of Examples 2 to 14 were prepared by the method of Example 1, according to the conditions shown in Table 1 below.
  • Dicyclopentadiene (DCPD) was dissolved in 500 ml of toluene as a solvent in a 1 L autoclave, and tricyclodecene (TCDE) as a polymerization regulator was added thereto.
  • An initiator was added thereto, and after the reactor was fastened, olefin was added, a catalyst was added to the mixture, and the reaction was performed. The reaction temperature was maintained at 40 ° C and the reaction was terminated after 2 hours. After completion of the reaction, the resulting petroleum resin was mixed with 300 g of water to separate the catalyst, and then distilled at 240 ° C. for 5 minutes to recover the unreacted oil to obtain the remaining petroleum resin.
  • Toluene was added 1.5 times as a hydrogenated solvent to 300 g of the obtained petroleum resin to completely dissolve and 1 L autoclave. 60 g of a palladium catalyst was added thereto, and hydrogenation was carried out for 90 minutes at a hydrogen pressure of 80 bar and a temperature of 230 ° C. after the fastening. After the reaction was completed, the reaction product was distilled at 250 °C for 5 minutes in a vacuum of 5torr to prepare a hydrogenated petroleum resin. Each detailed component was prepared in the content shown in Table 1.
  • the softening point was measured by Ring and ball softening method (ASTM E 28). Melt the resin into a ring-shaped mold, place it in a beaker containing glycerin, place the ball on the ring containing the resin, and raise the temperature by 2.5 °C per minute to raise the temperature (softening point) when the ball melts. It measured and described in Table 3.
  • Polystyrene reduced weight average molecular weight and number average molecular weight were measured by gel permeation chromatography (GPC) (PL GPC-220). Hydrogenated petroleum resin to be measured was dissolved in 1,2,4-trichlorobenzene so as to have a concentration of 0.34% by weight, and 288 ⁇ l was injected into GPC. The mobile phase of GPC used 1,2,4-trichlorobenzene and flowed in at a flow rate of 1 mL / min, the analysis was performed at 130 °C. The column was connected in series with two Guard columns and one PL 5 ⁇ l mixed-D. The detector was measured using a differential scanning calorimeter at a temperature of 10 ° C./min to 250 ° C., analyzed in N 2 atmosphere, and analyzed to 2nd scan.
  • GPC gel permeation chromatography
  • Mw shown in Table 3 means a weight average molecular weight, MWD means Mw / Mn.
  • the content (mol%) of olefins in hydrogenated petroleum resin can be analyzed from 1 H-NMR spectra through nuclear magnetic resonance spectroscopy (Bruker 500NMR, 14.1 telsa).
  • Color measurements were measured by ASTM D1544. Specifically, 10.0 g of hydrogenated petroleum resin was dissolved in 10.0 g of toluene, and then the cross section was placed in a rectangular quartz cell (5 cm wide, 4 cm long and 50 mm long). The cell was mounted with PFX195 COLORMETER and operated to measure APHA color.
  • Specific gravity was measured by ASTM D71. Specifically, 5 g of hydrogenated petroleum resin is dissolved in a hotplate at 200 ° C., poured into a sphere-shaped ring, and only the hydrogenated petroleum resin in a spherical form is removed from the ring and placed in a hydrometer (QUALITEST: Densimeter SD-200L) to measure specific gravity. It was.
  • the petroleum resin was evaluated for odor intensity for five men and women. 10 g of petroleum resin is placed in a 100 ml beaker and placed in an oven at 180 ° C. for 30 minutes. Remove the beaker from hot state and evaluate the odor generated from petroleum resin.
  • the odor intensity evaluation method directly smelled and classified by the values in the classification table of the following Table 2 to give a score from 0 to 5 points to measure the average score.
  • Examples 1 to 9 were prepared in a yield of 90% or more.
  • the odor is significantly improved when the compositions of all the examples are compared with the compositions of the comparative examples. Among them, it can be seen that excellent results are obtained when the C4 or more alkyl group is substituted as in Examples 1 to 12.
  • the method of preparing petroleum resin according to the present invention is different from the hydrogenation reaction after polymerization through a low temperature polymerization of about 40 ° C. in the presence of a cationic catalyst, which is a conventional method for producing petroleum resin, and high temperature heat of about 200 to 300 ° C. without a catalyst.
  • a cationic catalyst which is a conventional method for producing petroleum resin
  • high temperature heat of about 200 to 300 ° C. without a catalyst.
  • the compatibility, viscosity, and softening point used the method used by the resin characteristic evaluation method.
  • Open time was measured by JIT's hot melt tester. After applying a certain amount of adhesive to a cardboard 5 cm x 5 cm, and then attached to the cardboard 5 cm x 10 cm, the strength was increased from 0 to 5 seconds to record the force when the cardboard is detached. When the graph was drawn, the time at which it began to descend rapidly was recorded.
  • Measurement was made using a UTM instrument.
  • a tape was prepared by first applying a sample (adhesive) to the PET film to a thickness of 25 micrometers. It was attached to the SUS-304 steel plate. The portion where the PET film was attached was mounted on the UTM grip and measured at a speed of 30 mm / min. At this time, the value input to the UTM device means the adhesive force (kgf / in).
  • Adhesion was evaluated by the ASTM D3121 method.
  • test piece tape coated with 20-30 micrometers of adhesive was cut into 10 cm width and 50 cm length.
  • the ball tack tester JIS Z0237
  • the angle was set at a standard inclination angle of 30 degrees, and the steel ball No. 9 was rolled on it to measure the distance rolled. The less the ball rolls, the better the tack.
  • test piece tape coated with 20-30 micrometers of adhesive was cut out by 2 inches wide by 6 inches long.
  • the test piece was attached to a release paper, made into 1 inch wide and 2 inch long, and then attached to the cleaned SUS 304 steel sheet. (At this time, the non-stick test piece was attached to be about 2 cm or more. Roll was compressed by reciprocating once).
  • the test piece which did not adhere to the SUS 304 steel plate was cut with scissors so that it might become about 2 cm.
  • a test piece that did not adhere to the SUS 304 steel sheet was inserted into a ring for measuring Cohesion and bonded to the test piece that passed.
  • the front and back of the SUS 304 steel sheet to which the test piece is bonded with a fixing scotch tape were attached to each of the front and back in parallel, and two stamps were fixed between the ring for cohesion measurement and the SUS304 steel plate with a stamper. The remaining attached test piece was cut so that the test piece adhered to the SUS 304 steel plate by 1 inch in width and 1 inch in length.
  • Adhesion was evaluated by the ASTM D3654 method.
  • the specimen tape with 20-30 microns of adhesive was cut by 2 inches * 6 inches.
  • the test piece was attached to a release paper, made into 1 inch wide and 2 inch long, and then attached to the cleaned SUS 304 steel sheet. (At this time, the non-stick test piece was attached to be about 2 cm or more. Roll was compressed by reciprocating once).
  • the test piece which did not adhere to the SUS 304 steel plate was cut
  • a test piece that did not adhere to the SUS 304 steel sheet was inserted into a ring for measuring Cohesion and bonded to the test piece that passed.
  • the SUS 304 was fixed to the front and back of each of the SUS 304 steel sheet to which the test piece was bonded with a fixing scotch tape, and two pieces were placed in parallel between the hoop 304 and the SUS304 steel sheet. The remaining attached test piece was cut so that the test piece adhered to the SUS 304 steel plate by 1 inch in width and 1 inch in length.
  • Brookfield viscometer was used. A HT-2DB chamber was used and a sample of 10.5 was injected into Spindle No. 27. After heating up to the desired temperature for measurement, it had a stabilization time for 30 minutes. Viscosity values were recorded when the Torque had a 50% value, starting with 0.5 the stirring shaft RPM.
  • the softening point was measured by Ring and ball softening method (ASTM E 28). Melt the resin into a ring-shaped mold, place it in a beaker containing glycerin, place the ball on the ring containing the resin, and raise the temperature by 2.5 °C per minute to raise the temperature (softening point) when the ball melts. It measured and described in Table 3.
  • the production conditions were prepared by putting the raw materials of the four kinds (petroleum resin, polymer, oil, antioxidant) in a 100ml beaker and stirred at 180 ° C. for 4 hours, and detailed weight parts and characteristics evaluation results are shown in Table 5. At this time, * Aged in the following table shows the result of measurement after leaving each sample at 70 ° C. for 3 days.
  • the production conditions were prepared by putting the raw materials of the four kinds (petroleum resin, polymer, oil, antioxidant) in a 100ml beaker and stirring at 180 ° C. for 4 hours, and detailed weight parts and characteristics evaluation results are shown in Table 6.
  • Aged in the above table shows the result of measurement after leaving each sample at 70 °C for 3 days.
  • the production conditions were prepared by putting the raw materials of the four kinds (petroleum resin, polymer, oil, antioxidant) in a 100ml beaker and stirred at 180 ° C. for 4 hours, and detailed weight parts and characteristics evaluation results are shown in Table 7.
  • the production conditions were prepared by putting the four kinds of raw materials in a 100ml beaker and stirred for 1 hour at 180 °C, detailed weight parts and characteristics evaluation results are shown in Table 8.
  • the production conditions were prepared by putting the four kinds of raw materials in a 100ml beaker and stirred for 1 hour at 180 °C, the detailed weight parts and characteristics evaluation results are shown in Table 9.
  • Evonik's Vestoplast 703 (Amorphous propylene-ethylene copolymer) 40wt% as a polymer, Sasol C-80 (Sasol) 20wt% as a wax and 40wt% petroleum resin used in Examples and Comparative Examples Adhesives F (HMA) of Phosphorous Examples 2, 6, 7, 8, 13 and Comparative Examples 1, 2 and 4 were prepared.
  • the production conditions were prepared by putting the four kinds of raw materials in a 100ml beaker and stirred at 180 ° C. for 1 hour, and detailed weight parts and characteristics evaluation results are shown in Table 10 below.
  • the adhesive of the present invention increases adhesive strength, improves odor, and improves heat resistance.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne une résine de pétrole hydrogénée, et un procédé de production et son utilisation, et plus spécifiquement concerne une résine de pétrole hydrogénée produite en soumettant du dicyclopentadiène et un monomère oléfinique à une polymérisation thermique et ensuite la conduite d'une réaction d'hydrogénation, et concerne un procédé de production et son utilisation. La résine de pétrole hydrogénée présente l'avantage d'être utile dans les applications pratiques, dans la mesure où ladite résine de pétrole est produite via polymérisation thermique en utilisant des matières premières bon marché et, à l'opposé de la polymérisation classique avec un catalyseur, un procédé d'élimination de catalyseur peut être évité. La résine de pétrole hydrogénée produite de cette manière peut permettre l'utilisation, par exemple, comme agent adhésif utilisé dans les articles d'hygiène respectueux de l'environnement, que ladite résine de pétrole soit considérablement compatible, présente une forte viscosité et résistance à la chaleur tout en étant inodore.
PCT/KR2016/006905 2015-06-30 2016-06-28 Résine de pétrole hydrogénée, et son procédé de production et son utilisation Ceased WO2017003157A1 (fr)

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US15/740,641 US10647896B2 (en) 2015-06-30 2016-06-28 Hydrogenated petroleum resin, and production method and use therefor
JP2017568070A JP6827001B2 (ja) 2015-06-30 2016-06-28 水素添加石油樹脂、その製造方法及び用途
CN201680049664.4A CN107922552B (zh) 2015-06-30 2016-06-28 氢化石油树脂、其制备方法和用途
EP16818190.7A EP3318587A4 (fr) 2015-06-30 2016-06-28 Résine de pétrole hydrogénée, et son procédé de production et son utilisation
US16/839,383 US11186754B2 (en) 2015-06-30 2020-04-03 Hydrogenated petroleum resin, and production method and use therefor

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KR10-2015-0093774 2015-06-30
KR20150093774 2015-06-30
KR10-2015-0191077 2015-12-31
KR1020150191077A KR20170003367A (ko) 2015-06-30 2015-12-31 석유수지, 석유수지의 제조방법 및 접착제 조성물
KR1020160080204A KR101805892B1 (ko) 2015-06-30 2016-06-27 수소첨가 석유수지, 이의 제조방법 및 용도
KR10-2016-0080204 2016-06-27

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CN111989351A (zh) * 2018-03-28 2020-11-24 丸善石油化学株式会社 氢化石油树脂的除臭方法和氢化石油树脂的制造方法
EP3805273A4 (fr) * 2018-06-11 2022-05-11 Hanwha Solutions Corporation Procédé de production de résine hydrocarbonée
EP3805283A4 (fr) * 2018-06-11 2022-05-18 Hanwha Solutions Corporation Procédé de production de résine à base de dicyclopentadiène

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JPH051292A (ja) * 1990-07-18 1993-01-08 Maruzen Petrochem Co Ltd トラクシヨンドライブ用流体
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KR880000504A (ko) * 1986-06-14 1988-03-26 시마다 에이죠 고무 배합물질 및 조성물
JPH051292A (ja) * 1990-07-18 1993-01-08 Maruzen Petrochem Co Ltd トラクシヨンドライブ用流体
JP2009256504A (ja) * 2008-04-18 2009-11-05 Jsr Corp 射出成形体形成用樹脂組成物および射出成形体
KR20140020991A (ko) * 2011-06-01 2014-02-19 이데미쓰 고산 가부시키가이샤 수소 첨가 석유 수지 펠릿의 제조 방법
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111989351A (zh) * 2018-03-28 2020-11-24 丸善石油化学株式会社 氢化石油树脂的除臭方法和氢化石油树脂的制造方法
EP3805273A4 (fr) * 2018-06-11 2022-05-11 Hanwha Solutions Corporation Procédé de production de résine hydrocarbonée
EP3805283A4 (fr) * 2018-06-11 2022-05-18 Hanwha Solutions Corporation Procédé de production de résine à base de dicyclopentadiène

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