A low-VOC bio-based modified DCPD hydrogenated resin device and synthesis process and its application in pressure-sensitive adhesive hot melt adhesive

Abstract

The present invention relates to a low-VOC bio-based modified DCPD hydrogenated resin device and synthesis process and its application in pressure-sensitive adhesive hot melt adhesive. Using whole distillation cracked C5 as raw material, the alkynes in the whole distillation cracked C5 raw material are prepolymerized by controlling the low temperature and residence time to generate C15 to C20 polymers. The molecular weight of the generated resin is concentrated, which solves the problem of the excessively fast polymerization rate and high activity of alkynes to produce explosive polymers and insoluble slags that affect the system and products, and improves the utilization rate of raw materials. A continuous polymerization process is adopted to convert all dicyclopentadiene monomers into DCPD resin, and the content of unpolymerized monomers is low, which reduces the energy consumption generated by the large-scale application of unpolymerized monomers. The introduction of bio-based monomers in the polymerization process makes up for the disadvantage of the lack of polar groups in the molecular structure of DCPD resin. At the same time, the introduction of vinyl cyclohexene increases the grafting rate of bio-based monomers, solving the application problem of poor compatibility between DCPD resin and elastomer.

Description

Technical Field

[0001] The invention relates to the technical field of petroleum resin hydrogenation, and more specifically to a low-VOC bio-based modified DCPD hydrogenation resin device and a synthesis process and an application thereof in pressure-sensitive adhesives and hot-melt adhesives. Background Art

[0002] Hydrogenation modification is an important method for modifying petroleum resins, among which DCPD (dicyclopentadiene) resin can be used to produce high-grade gold powder, silver powder ink, ink color developer and linker, etc. For petroleum resins, especially DCPD petroleum resins with a ring structure, the molecular weight is large, and the polymer molecules extend on the catalyst surface, forming a high steric hindrance. Its molecular structure determines that it is difficult to hydrogenate petroleum resins. The conventional DCPD hydrogenation (dicyclopentadiene hydrogenation) resin formula is: crude dicyclopentadiene, isopentylene monomer and inert polymerization solvent are intermittently thermally polymerized in a hot polymerization reactor to prepare DCPD resin, and then hydrogenated by a palladium catalyst to obtain DCPD hydrogenated resin.

[0003] CN1189493C introduces a hydrogenation catalyst for preparing dicyclopentadiene hydrogenated petroleum resin. Pt is added to the catalyst, which is expensive and the softening point of the obtained product is seriously reduced. In addition, the process is carried out in a reactor, the catalyst is difficult to separate, and catalyst residues are present in the resin. CN1189494C introduces a method for hydrogenating dicyclopentadiene petroleum resin. The process is a kettle reactor, the catalyst is difficult to separate, catalyst residues are present in the resin, and the catalyst is expensive. CN103360547B introduces a system and method for producing dicyclopentadiene hydrogenated petroleum resin. Although the entire resin hydrogenation process is introduced, it is still a kettle reaction, the catalyst is difficult to separate, and catalyst residues are present in the resin. Summary of the invention

[0004] The invention provides a low-VOC bio-based modified DCPD hydrogenated resin device, which comprises: a prepolymerization kettle, a deweighting tower, a dimerization kettle, a separation tower, a first static mixer, a batching tank, a second static mixer, a mixing tank, a hot polymerization kettle, a third static mixer, a polymerization kettle, a raw material tank, a reactor, a coiled tube heat exchanger, a stripping tower and an oil-water separator; the prepolymerization kettle is connected to the deweighting tower, the top of the deweighting tower is connected to the dimerization kettle, the bottom of the deweighting tower is connected to the first static mixer, the prepolymerization kettle, the deweighting tower, the dimerization kettle, the separation tower, the first static mixer, the batching tank, the third static mixer, the polymerization kettle, the raw material tank and the reactor are connected in sequence; the second static mixer, the mixing tank and the hot polymerization kettle are connected in sequence; the coiled tube heat exchanger, the stripping tower and the oil-water separator are connected in sequence.

[0005] The outlet of the reactor is connected to the inlet of the coiled-tube heat exchanger; the lower outlet of the oil-water separator is the outlet of the steam condensate, and the upper outlet is connected to the inlet of the first static mixer.

[0006] One end of the lower outlet of the thermal polymerization kettle is connected to the inlet of the second static mixer, and the other end is connected to the inlet of the third static mixer.

[0007] The present invention provides a process for synthesizing a low-VOC bio-based modified DCPD hydrogenated resin using the device, comprising the following steps:

[0008] Step 1: The whole fraction cracked C5 raw material is first introduced into a prepolymerization kettle and then into a de-weighting tower. The C15 to C20 polymers at the bottom of the de-weighting tower are introduced into a batching tank through a first static mixer to participate in subsequent reactions. The cracked C5 raw material is obtained at the top of the de-weighting tower and enters a dimerization kettle. The prepolymerization kettle polymerizes the alkynes in the whole fraction cracked C5 raw material into C15 to C20 polymers. The remaining cracked C5 raw material is then self-polymerized into a DCPD raw material by a dimerization kettle. The light component de-ringed C5 is separated from the top of the tower by a separation tower to obtain DCPD in the kettle.

[0009] Step 2: Vinyl cyclohexene and bio-based monomers such as fumaric acid or itaconic acid or a mixture thereof are introduced into a second static mixer for premixing, then introduced into a mixing tank for uniform mixing, and then introduced into a hot polymerization kettle for reaction to obtain a copolymer intermediate, and the unreacted raw materials are returned to the second static mixer through a bottom circulation pump of the hot polymerization kettle;

[0010] Step 3: piperylene is introduced into the first static mixer, and is introduced into the third static mixer with the DCPD obtained in step 1 through the first static mixer and the batching tank in sequence, and the copolymer intermediate obtained in step 2 is introduced into the third static mixer and mixed with DCPD, and then introduced into the polymerization kettle together for polymerization reaction to obtain a modified DCPD resin;

[0011] Step 4: The modified DCPD resin is introduced into the reactor through the raw material tank, and hydrogen is introduced into the reactor at the same time. The reaction product is heated in a coiled tube heat exchanger and then enters a stripping tower for stripping. At the same time, steam is introduced into the stripping tower kettle. The top product of the stripping tower enters the first static mixer for circulation through an oil-water separator, and a low-VOC bio-based modified DCPD hydrogenated resin is obtained in the stripping tower kettle.

[0012] The fully distilled cracked carbon is polymerized in a prepolymerization kettle with a residence time of 1-5 hours, a polymerization pressure of 0.8-2.0 MPa, and a polymerization temperature of 40-80°C.

[0013] Traditional cracked C5 contains some alkynes, which are prone to explosion and formation of explosives in the direct synthesis process, making it difficult to hydrogenate the product. The finished resin is dark in color, has poor heat resistance, has a wide molecular weight distribution, and has poor compatibility with elastomers. The conventional process chooses to remove alkynes first and then copolymerize, but the alkyne removal step is energy-intensive and will cause some dienes to be removed as well, reducing the conversion rate of the raw materials. At the same time, the current C5 resin has poor polarity, does not contain polar groups and rigid ring structures in the molecular weight, has poor cohesion and rigidity, and cannot be used in high-performance adhesives and plastic modifications. This application study found that using full-distillation cracked C5 as a raw material, the material residence time in the prepolymerization kettle is limited to 1-5 hours, the polymerization pressure is 0.8-2.0MPa, and the polymerization temperature is 40-80°C. A prepolymerization kettle is set up to prepolymerize the alkynes in the full-distillation cracking C5 raw material to generate C15 to C20 polymers. The resin molecular weight is concentrated rather than large molecular explosive polymers. This solves the problem of the excessively fast polymerization rate and high activity of alkynes producing explosive polymers and insoluble slag that affect the system and products. At the same time, it improves the raw material utilization rate and reduces energy consumption and production costs.

[0014] The material stays in the dimer for 0.5-3 hours, the pressure is 0.8-2.0 MPa, and the polymerization temperature is 220-270°C.

[0015] The operating pressure of the separation tower is 80-90 kPa, and the top temperature is 110-120°C.

[0016] The copolymerization temperature is 180-220° C. and the pressure is 0.2-1.0 MPa.

[0017] The pressure of the polymerization kettle is 1.0-2.5MPa, the polymerization temperature is 215-285°C, the agitator speed is 120-150 rpm, one end of the polymerization kettle outlet returns to the third static mixer for circulation, and the other end enters the raw material tank, and the weight ratio of the material circulating back to the third static mixer to the material entering the raw material tank is 10:1~30:1.

[0018] The present application has found that by adopting a continuous polymerization process, by setting up multiple static mixers and controlling the reaction parameters of the polymerization kettle, one end of the polymerization kettle outlet returns to the third static mixer for circulation, and the other end enters the raw material tank, and the weight ratio of the material circulating back to the third static mixer to the material entering the raw material tank is 10:1 to 30:1. The dicyclopentadiene monomer, isopentylene monomer and the applied polymerization solvent can be fully mixed, so that the thermal polymerization reaction is more complete and thorough, and the dicyclopentadiene monomer is completely converted into DCPD resin, the unpolymerized monomer content is low, and the energy consumption generated by the large-scale application of unpolymerized monomers is reduced.

[0019] The reaction temperature of the reactor is 140-200°C, the operating pressure is 6.0-10.0MPa, and the space velocity is 1.0-2.0h-1 , the volume ratio of hydrogen to modified DCPD resin is (200-400):1.

[0020] The heating temperature of the coil heat exchanger is 250-270° C., and the pressure of the stripping tower is -90 kPa to -98 kPa.

[0021] The bio-based monomer includes at least one of fumaric acid and itaconic acid.

[0022] The weight ratio of DCPD, vinyl cyclohexene and bio-based monomers such as fumaric acid or itaconic acid or a mixture thereof is (70-90): (5-20): (5-15).

[0023] Preferably, the weight ratio of DCPD, vinyl cyclohexene and bio-based monomers such as fumaric acid or itaconic acid or a mixture thereof is (77-90): (5-15): (5-10).

[0024] The research of this application found that the weight ratio of DCPD, vinyl cyclohexene and bio-based monomers such as fumaric acid or itaconic acid or their mixtures is (70-90): (5-20): (5-15). By introducing the highly active double bonds of vinyl cyclohexene (VCH) and copolymerizing with bio-based monomers such as fumaric acid or itaconic acid or their mixtures, the intermediate formed is then polymerized with DCPD, which can greatly improve the grafting rate of bio-based monomers in DCPD resin, make up for the disadvantage of lack of polar groups in the molecular structure of DCPD resin, solve the application problem of poor compatibility of DCPD resin with elastomers, and thus improve the quality of petroleum resin products. The double bond of bio-based monomers such as fumaric acid or itaconic acid is sandwiched between two carboxyl groups. During graft polymerization, the steric hindrance is large, the activity of direct polymerization with DCPD is low, and the grafting rate is low. This patent introduces vinyl cyclohexene (VCH), a cyclic diene medium. On the one hand, VCH contains a six-membered ring structure, and the steric hindrance is smaller than that of DCPD, but it still has a certain steric hindrance effect, which can prevent the molecular weight of the copolymer from being too large. The other part of the ring structure also contains active double bonds, which can form copolymers with C5 olefins under the action of thermal initiation.

[0025] The step 4 adopts a fixed bed hydrogenation process, and the reactor is provided with a catalyst layer (Raney nickel catalyst, manufactured by Shanghai Xunkai New Materials Technology Co., Ltd., FAMC-1900).

[0026] The weight ratio of the DCPD to isobutylene is 100:(1-5).

[0027] Preferably, the weight ratio of DCPD to piperylene is 100:(1.5-2.5).

[0028] The applicant has found that the weight ratio of DCPD to isobutylene is 100:(1-5), which makes the molecular weight of the bio-modified DCPD resin concentrated, thereby reducing the difficulty of hydrogenation. The finished resin has light color, strong heat resistance, and good compatibility with elastomers. At the same time, due to the full polymerization of the active components, the yield of the resin is improved, and the proportion of the resin used in high-performance adhesives and plastic modifications is increased.

[0029] Preferably, the weight ratio of the whole distillation cracked C5 to DCPD is 100:(14-20).

[0030] The invention provides an application of a synthesis process of a low-VOC bio-based modified DCPD hydrogenated resin. The synthesized bio-based modified DCPD hydrogenated resin is applied to one of a pressure-sensitive adhesive and a hot-melt adhesive.

[0031] Calculated by weight percentage, the formula of the pressure-sensitive adhesive includes: 20-50% of SIS block copolymer, 10-30% of filler oil, and the balance is made up of low-VOC bio-based modified DCPD hydrogenated resin.

[0032] Preferably, the formula of the pressure-sensitive adhesive comprises, by weight percentage: 20-40% SIS block copolymer, 10-25% filler oil, and the balance made up by low VOC bio-based modified DCPD hydrogenated resin.

[0033] Further preferably, the formula of the pressure-sensitive adhesive comprises, by weight percentage: 25-35% of SIS block copolymer, 10-20% of filler oil, and the balance made up by low VOC bio-based modified DCPD hydrogenated resin.

[0034] The extender oil includes at least one of liquid paraffin, dibutyl phthalate, lanolin, castor oil and naphthenic oil.

[0035] Calculated by weight percentage, the formula of the hot melt adhesive includes: 20-50% of ethylene-vinyl acetate copolymer, 20-40% of lubricant, and low-VOC bio-based modified DCPD hydrogenated resin making up the balance.

[0036] Preferably, the formula of the hot melt adhesive comprises, by weight percentage: 20-50% ethylene-vinyl acetate copolymer, 20-35% lubricant, and the balance is made up of low VOC bio-based modified DCPD hydrogenated resin.

[0037] Further preferably, the formula of the hot melt adhesive comprises, by weight percentage: 25-50% ethylene-vinyl acetate copolymer, 25-35% lubricant, and the balance made up by low VOC bio-based modified DCPD hydrogenated resin.

[0038] The lubricant is at least one of polyethylene wax, Fischer-Tropsch wax, microcrystalline wax, polypropylene wax and Sasol wax.

[0039] Beneficial effects:

[0040] 1. The present application uses whole distillation cracked carbon five as raw material, limits the residence time of the material in the prepolymerization kettle to 1-5 hours, the polymerization pressure to 0.8-2.0 MPa, the polymerization temperature to 40-80°C, and sets a prepolymerization kettle to prepolymerize the alkynes in the whole distillation cracked carbon five raw material, thereby solving the problem of the excessively fast polymerization rate and high activity of alkynes, which produces explosive products and insoluble slag that affect the system and products, and at the same time improves the raw material utilization rate and reduces energy consumption and production costs.

[0041] 2. A continuous polymerization process is adopted. By setting up multiple static mixers and controlling the reaction parameters and circulation of the polymerization kettle, the dicyclopentadiene monomer, isopentadiene monomer and the applied polymerization solvent can be fully mixed, so that the thermal polymerization reaction is more complete and thorough, and the dicyclopentadiene monomer is completely converted into DCPD resin. The content of unpolymerized monomer is low, reducing the energy consumption caused by the large-scale application of unpolymerized monomers.

[0042] 3. The weight ratio of DCPD, vinyl cyclohexene and bio-based monomers such as fumaric acid or itaconic acid or their mixtures is (70-90): (5-20): (5-15), which can greatly improve the grafting rate of bio-based monomers in DCPD resin, make up for the disadvantage of lack of polar groups in the molecular structure of DCPD resin, solve the application problem of poor compatibility between DCPD resin and elastomer, and thus improve the quality of petroleum resin products.

[0043] 4. The present application adopts a fixed bed hydrogenation process and uses a large pore volume and multi-pore size Raney nickel catalyst to adapt to the macromolecular polymer formed by polymerization, saturate the dienes and most of the monoolefins in the DCPD resin, retain the hydroxyl structure brought by the bio-based group, and increase the polarity of the DCPD hydrogenated resin.

[0044] 5. In the present application, most of the oligomers in the DCPD hydrogenated resin are extracted through steam stripping process, high vacuum and high negative pressure process, high temperature and high flow rate coil heat exchanger heating, etc., after hydrogenated DCPD resin is heated in an oven at 200°C for 2 hours, and the oligomer residue is calibrated to be less than 1.3%, and the odor is significantly less than that of similar products.

[0045] 6. The molecular weight of the bio-based modified DCPD resin of the present application is concentrated, the difficulty of product hydrogenation is reduced, the finished resin has light color, strong heat resistance, and good compatibility with elastomers. At the same time, due to the full polymerization of the active components, the yield of the resin is improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] Figure 1 This is the device diagram of Example 1.

[0047] Among them, 1. prepolymerization kettle; 2. deweighting tower; 3. dimerization kettle; 4. separation tower; 5. first static mixer; 6. batching tank; 7. second static mixer; 8. mixing tank; 9. hot polymerization kettle; 10. third static mixer; 11. polymerization kettle; 12. raw material tank; 13. reactor; 14. coil heat exchanger; 15. stripping tower; 16. oil-water separator. DETAILED DESCRIPTION

[0048] Example 1

[0049] A low VOC bio-based modified DCPD hydrogenation resin device, such as Figure 1 As shown, the device comprises: a prepolymerization kettle 1, a deweighting tower 2, a dimerization kettle 3, a separation tower 4, a first static mixer 5, a batching tank 6, a second static mixer 7, a mixing tank 8, a hot polymerization kettle 9, a third static mixer 10, a polymerization kettle 11, a raw material tank 12, a reactor 13, a coiled heat exchanger 14, a stripping tower 15 and an oil-water separator 16; the prepolymerization kettle 1 is connected to the deweighting tower 2, the top of the deweighting tower 2 is connected to the dimerization kettle 3, the bottom of the deweighting tower 2 is connected to the first static mixer 5, the prepolymerization kettle 1, the deweighting tower 2, the dimerization kettle 3, the separation tower 4, the first static mixer 5, the batching tank 6, the third static mixer The reactor 10, the polymerization kettle 11, the raw material tank 12, and the reactor 13 are connected in sequence; the second static mixer 7, the mixing tank 8, and the hot polymerization kettle 9 are connected in sequence; the coil heat exchanger 14, the stripping tower 15 and the oil-water separator 16 are connected in sequence; the outlet of the reactor 13 is connected to the inlet of the coil heat exchanger 14; the lower outlet of the oil-water separator 16 is the discharge port of the steam condensate, and the upper outlet is connected to the inlet of the first static mixer 5; one end of the lower outlet of the hot polymerization kettle 9 is connected to the inlet of the second static mixer 7, and the other end is connected to the inlet of the third static mixer 10; the connections are all connected through pipelines.

[0050] The reactor 13 is provided with a catalyst layer (Raney nickel catalyst, manufactured by Shanghai Xunkai New Materials Technology Co., Ltd., FAMC-1900).

[0051] A process for synthesizing a low-VOC bio-based modified DCPD hydrogenated resin using the device comprises the following steps:

[0052] Step 1: The whole fraction cracked C5 raw material is first introduced into the prepolymerization kettle 1 and then into the de-weighting tower 2. The C15 to C20 polymers at the bottom of the de-weighting tower 2 pass through the first static mixer 5 and enter the batching tank 6 to participate in the subsequent reaction. The cracked C5 raw material is obtained at the top of the de-weighting tower 2 and enters the dimerization kettle. The prepolymerization kettle polymerizes the alkynes in the whole fraction cracked C5 raw material into C15 to C20 polymers. The CPD in the remaining cracked C5 raw material is self-polymerized into DCPD raw material through the dimerization kettle 3. The light component de-ringed C5 is separated from the top of the tower through the separation tower 4 to obtain DCPD in the kettle.

[0053] Step 2: Vinyl cyclohexene (Henghe Materials Technology Co., Ltd.) and fumaric acid and itaconic acid bio-based monomers are introduced into the second static mixer 7 for premixing, and then introduced into the mixing tank 8 for uniform mixing, and then introduced into the hot polymerization kettle 9 for reaction to obtain a copolymer intermediate, and the unreacted raw materials are returned to the second static mixer 7 through the bottom circulation pump of the hot polymerization kettle 9;

[0054] Step 3: piperylene (Henghe (Nanjing) Materials Technology Co., Ltd.) is introduced into the first static mixer 5, and the DCPD obtained in step 1 is sequentially introduced into the third static mixer 10 through the first static mixer 5 and the batching tank 6, and the copolymer intermediate obtained in step 2 is introduced into the third static mixer 10 and mixed with DCPD, and then introduced into the polymerization kettle 11 for polymerization reaction to obtain a modified DCPD resin;

[0055] Step 4: The modified DCPD resin is introduced into the reactor 13 through the raw material tank 12, and hydrogen is introduced into the reactor 13 at the same time. The reaction product is introduced into the coil heat exchanger 14 for heating and then enters the stripping tower 15 for stripping. At the same time, steam is introduced into the bottom of the stripping tower 15. The top product of the stripping tower 15 enters the first static mixer 5 for circulation through the oil-water separator 16. Steam is injected into the bottom of the stripping tower 15 to flash the solvent and oligomers in the hydrogenated resin through negative pressure stripping, and a low-VOC bio-based modified DCPD hydrogenated resin is obtained in the bottom of the stripping tower 15.

[0056] The fully distilled cracked carbon is polymerized in the prepolymerization kettle 1 with a residence time of 3 hours, a polymerization pressure of 1.4 MPa and a polymerization temperature of 60°C.

[0057] The material stayed in the dimer 3 for 1.75 hours, the pressure was 0.9 MPa, and the polymerization temperature was 245°C.

[0058] The operating pressure of the separation tower 4 is 85 kPa, and the tower top temperature is 115°C.

[0059] The copolymerization pressure is 0.6 MPa.

[0060] The pressure of the polymerization kettle 11 is 1.75 MPa, the polymerization temperature is 260°C, the agitator speed is 135 rpm, one end of the outlet of the polymerization kettle 11 returns to the third static mixer 10 for circulation, and the other end enters the raw material tank 12. The weight ratio of the material circulating back to the third static mixer 10 to the material entering the raw material tank 12 is 20:1.

[0061] The reaction temperature of the reactor 13 is 170°C, the operating pressure is 8.0 MPa, and the space velocity is 1.5 h -1 , the volume ratio of hydrogen to modified DCPD resin is 300:1.

[0062] The heating temperature of the coil heat exchanger 14 is 260° C., and the pressure of the stripping tower 15 is −94 kPa.

[0063] The copolymerization temperature is 180° C., the bio-based monomer is fumaric acid, and the weight ratio of DCPD, vinyl cyclohexene and bio-based monomer is 90:5:5.

[0064] The weight ratio of the DCPD to piperylene is 100:2.

[0065] The weight ratio of the fully distilled cracked C5 to DCPD is 100:17.

[0066] Example 2

[0067] A low VOC bio-based modified DCPD hydrogenation resin device, same as Example 1.

[0068] A process for synthesizing low-VOC bio-based modified DCPD hydrogenated resin using the device is the same as Example 1.

[0069] The invention discloses an application of a synthesis process of a low-VOC bio-based modified DCPD hydrogenated resin for use in pressure-sensitive adhesives.

[0070] Calculated by weight percentage, the formula of the pressure-sensitive adhesive includes: 30% of SIS block copolymer, 20% of filler oil (naphthenic oil, Karamay KN4010), and the balance is made up of low-VOC bio-based modified DCPD hydrogenated resin.

[0071] Example 3

[0072] The specific implementation is the same as that of Example 2, except that the bio-based monomer is itaconic acid.

[0073] Example 4

[0074] The specific implementation is the same as Example 2, except that: the bio-based monomer is fumaric acid; and the weight ratio of DCPD, vinyl cyclohexene and bio-based monomer is 85:10:5.

[0075] Example 5

[0076] The specific implementation is the same as Example 2, except that: the bio-based monomer is fumaric acid; and the weight ratio of DCPD, vinyl cyclohexene and bio-based monomer is 80:15:5.

[0077] Example 6

[0078] The specific implementation is the same as Example 2, except that: the bio-based monomer is fumaric acid; and the weight ratio of DCPD, vinyl cyclohexene and bio-based monomer is 82:10:8.

[0079] Example 7

[0080] The specific implementation is the same as Example 2, except that: the copolymerization temperature is 190° C., the bio-based monomer is fumaric acid; and the weight ratio of DCPD, vinyl cyclohexene and bio-based monomer is 77:15:8.

[0081] Example 8

[0082] The specific implementation is the same as Example 2, except that: the copolymerization temperature is 200° C., the bio-based monomer is fumaric acid; and the weight ratio of DCPD, vinyl cyclohexene and bio-based monomer is 77:15:8.

[0083] Example 9

[0084] A low VOC bio-based modified DCPD hydrogenation resin device, same as Example 1.

[0085] A process for synthesizing low-VOC bio-based modified DCPD hydrogenated resin using the device is the same as Example 1.

[0086] Application of a synthesis process of low VOC bio-based modified DCPD hydrogenated resin for hot melt adhesives:

[0087] Measured by weight percentage, the formula of the hot melt adhesive includes: 30% ethylene-vinyl acetate copolymer (Hanhua-1528), 30% lubricant (microcrystalline wax, universal microcrystalline wax with a melting point of 58°C), and the balance is made up of low-VOC bio-based modified DCPD hydrogenated resin.

[0088] Example 10

[0089] The specific implementation is the same as that of Example 9, except that the bio-based monomer is itaconic acid.

[0090] Embodiment 11

[0091] The specific implementation is the same as Example 9, except that: the bio-based monomer is fumaric acid; and the weight ratio of DCPD, vinyl cyclohexene and bio-based monomer is 85:10:5.

[0092] Example 12

[0093] The specific implementation is the same as Example 9, except that: the bio-based monomer is fumaric acid; and the weight ratio of DCPD, vinyl cyclohexene and bio-based monomer is 80:15:5.

[0094] Example 13

[0095] The specific implementation is the same as Example 9, except that: the bio-based monomer is fumaric acid; and the weight ratio of DCPD, vinyl cyclohexene and bio-based monomer is 82:10:8.

[0096] Embodiment 14

[0097] The specific implementation is the same as Example 9, except that: the copolymerization temperature is 190° C., the bio-based monomer is fumaric acid; and the weight ratio of DCPD, vinyl cyclohexene and bio-based monomer is 77:15:8.

[0098] Embodiment 15

[0099] The specific implementation is the same as Example 9, except that: the copolymerization temperature is 200° C., the bio-based monomer is fumaric acid; and the weight ratio of DCPD, vinyl cyclohexene and bio-based monomer is 77:15:8.

[0100] Comparative Example 1

[0101] The specific implementation method is the same as that of Example 2; the difference is that in Comparative Example 1: Step 2 specifically includes introducing the bio-based monomer into a second static mixer (7) for premixing, then introducing the bio-based monomer into a mixing tank (8) for uniform mixing, and then introducing the bio-based monomer into a hot polymerization kettle (9) for reaction to obtain a copolymer intermediate, and the unreacted raw material is returned to the second static mixer (7) through the bottom circulation pump of the hot polymerization kettle (9).

[0102] Comparative Example 2

[0103] The specific implementation method is the same as that of Example 9; the difference is that in Comparative Example 2: Step 2 specifically includes introducing the bio-based monomer into a second static mixer (7) for premixing, then introducing the bio-based monomer into a mixing tank (8) for uniform mixing, and then introducing the bio-based monomer into a hot polymerization kettle (9) for reaction to obtain a copolymer intermediate, and the unreacted raw material is returned to the second static mixer (7) through the bottom circulation pump of the hot polymerization kettle (9).

[0104] Comparative Example 3

[0105] Competitors

[0106] Applied to pressure-sensitive adhesive, the formula of the pressure-sensitive adhesive includes, by weight percentage: 30% SIS block copolymer, 20% filler oil (naphthenic oil, Karamay KN4010), and the balance is made up by competitor resin.

[0107] Comparative Example 4

[0108] Competitors

[0109] Application in hot melt adhesive:

[0110] Calculated by weight percentage, the formula of the hot melt adhesive includes: 30% ethylene-vinyl acetate copolymer (Hanwha-1528), 30% lubricant (microcrystalline wax, universal microcrystalline wax with a melting point of 58°C), and the balance is made up of competitor resin.

[0111] Performance Testing Methods

[0112] 1. Physical and chemical properties test of low VOC bio-based modified DCPD hydrogenated resin (Table 1)

[0113] 1. Alcohol conversion rate:

[0114] The residual amount of alcohol in the unpolymerized solvent is determined by gas / liquid chromatography. The difference between the residual amount and the amount of alcohol added in the raw material is the total amount of alcohol converted. The ratio of the total amount of alcohol converted to the amount added is the alcohol conversion rate in the synthesis process.

[0115] 2. Chroma:

[0116] The color test standard is ASTM-D6166

[0117] 3. Volatile amount of oligomers at 200℃:

[0118] Accurately weigh the sample and add it to the crucible. Heat the crucible with the sample in a 200℃ forced air oven for 2 hours. Take out the crucible, cool it, and weigh it. The reduced weight is the oligomer content, and the ratio of the reduced weight to the added amount of the sample is the volatile amount of the oligomer at 200℃, which is measured in percentage.

[0119] The "-" is not tested.

[0120] 2. Hot melt adhesive and pressure sensitive adhesive performance test

[0121] 1. Prepare the sample

[0122] Preparation method of pressure-sensitive adhesive: add cyclopentane oil and elastomer into a planetary mixer, start to introduce constant temperature heat transfer oil to increase the temperature, control the temperature in the mixer kettle at 160°C, start stirring, and the stirring speed is 150r / min. After stirring for 30 minutes, the elastomer is completely dissolved in the cyclopentane oil. Open the mixer kettle cover, add low-VOC bio-based modified DCPD hydrogenated resin, keep the temperature in the kettle unchanged, continue stirring for 40 minutes, stop heating, and when the temperature in the kettle drops to 130°C, discharge the material to prepare a pressure-sensitive adhesive block.

[0123] Preparation method of hot melt adhesive: add all raw materials into a planetary mixer, start to introduce constant temperature heat transfer oil to increase the temperature, control the temperature in the mixer kettle at 150℃, start stirring, the stirring speed is 150r / min, after stirring for 30 minutes, cool the adhesive to 140℃, discharge the material, and obtain hot melt adhesive.

[0124] After the hot melt adhesive block and pressure-sensitive adhesive block are prepared, they are coated. A hot melt adhesive coating machine is used to melt the adhesive block. The melting temperature is 145°C. The melted adhesive liquid is scraped to control the film thickness to 30 microns. After cutting to a fixed size according to the test size, it is cured for 24 hours at 25°C and a humidity of 50±5% before performance testing can be carried out.

[0125] 2. Performance test (hot melt adhesive: Table 2; pressure sensitive adhesive: Table 3)

[0126] Initial adhesion test standard GB / T4852-2002.

[0127] Adhesion test standard GB / T4851-2014.

[0128] Peel strength test standard GB / T2792-2014.

[0129] Open time test method: put the prepared hot melt adhesive into a glue cup and re-melt it in a constant temperature oven at 180℃. At the same time, prepare 20 paper strips of uniform size and a stopwatch. Take out the molten hot melt adhesive sample after about 30 minutes, and immediately use an applicator to apply the hot melt adhesive to the kraft paperboard to form a rectangular adhesive application area. At the same time, press the stopwatch to start timing. Place a paper strip in the adhesive application area every one second. After all the paper strips are placed, pick them up one by one from the paper strip with the longest placement time until the placement time corresponding to the stuck paper strip is found, which is the open time. This method is to test the maximum time interval that the hot melt adhesive can still bond to the substrate after being applied to the surface. Completing the bonding within the open time can ensure that the hot melt adhesive achieves the best bonding effect.

[0130] Performance test data

[0131] Table 1

[0132] Comparative Example 3 Comparative Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Alcohol conversion rate% - 5.4 7.63 2.65 10.8 13.6 15.3 17 17.5 Chroma 0.5 0.5 0.5 0.5 0.5 0.5 0.6 0.7 0.9 200℃ Oligomer Volatilization % 3.2 1.3 1.25 1.33 1.27 1.1 1.29 1.17 1.22

[0133] Table 2

[0134] Comparative Example 3 Comparative Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Initial adhesion (g) 3105 3258 3425 3205 3455 3514 3674 3855 3892 Peel strength (N) 29 31.5 33 29.5 33.2 35 35.5 37.2 37.5 Holding force (g) 33.5 34.9 35.2 33.7 35.7 36.2 36 38.4 38.5

[0135] Table 3

[0136] Comparative Example 4 Comparative Example 2 Example 9 Example 10 Embodiment 11 Example 12 Example 13 Embodiment 14 Embodiment 15 Peel strength (N) 27.5 29.4 31 27.3 32 32.7 33 34.2 34.5 Holding force (g) 32 33 34.2 32.5 34.2 35.9 37.5 38.3 39 Opening hours(s) 10.5 11 11 13 12 12 13 15 15 Peel strength, 90%RH / 60℃ (KN.m) 2.3 3.2 4.9 2.5 5.2 5.7 6 7.4 7.5

Claims

1. A process for preparing a low VOC bio-based modified DCPD hydrogenated resin, characterized in that: The device used in the process comprises: a prepolymerization kettle (1), a deweighting tower (2), a dimerization kettle (3), a separation tower (4), a first static mixer (5), a batching tank (6), a second static mixer (7), a mixing tank (8), a hot polymerization kettle (9), a third static mixer (10), a polymerization kettle (11), a raw material tank (12), a reactor (13), a coiled heat exchanger (14), a stripping tower (15) and an oil-water separator (16); the prepolymerization kettle (1) is connected to the deweighting tower (2), and the deweighting tower (2) is The top of the tower is connected to the dimerizer (3); the bottom of the deweighting tower (2) is connected to the first static mixer (5); the dimerizer (3), the separation tower (4), the first static mixer (5), the batching tank (6), the third static mixer (10), the polymerization kettle (11), the raw material tank (12), and the reactor (13) are connected in sequence; the second static mixer (7), the mixing tank (8), and the hot polymerization kettle (9) are connected in sequence; the coil heat exchanger (14), the stripping tower (15), and the oil-water separator (16) are connected in sequence; The outlet of the reactor (13) is connected to the inlet of the coiled heat exchanger (14); the lower outlet of the oil-water separator (16) is a discharge port for steam condensate, and the upper outlet is connected to the inlet of the first static mixer (5); One end of the lower outlet of the thermal polymerization kettle (9) is connected to the inlet of the second static mixer (7), and the other end is connected to the inlet of the third static mixer (10); The preparation process comprises the following steps: Step 1: The whole fraction cracked C5 raw material is first introduced into a prepolymerization kettle (1) and then into a de-weighting tower (2). The C15 to C20 polymers at the bottom of the de-weighting tower (2) pass through a first static mixer (5) and enter a batching tank (6) to participate in subsequent reactions. The cracked C5 raw material is obtained at the top of the de-weighting tower (2) and enters a dimerization kettle (3). The prepolymerization kettle polymerizes the alkynes in the whole fraction cracked C5 raw material into C15 to C20 polymers. The remaining cracked C5 raw material is then passed through a dimerization kettle (3) to self-polymerize CPD into a DCPD raw material. The light component de-ringed C5 is then separated from the top of the tower through a separation tower (4) to obtain DCPD in the bottom of the tower. Step 2: Vinylcyclohexene, fumaric acid and / or itaconic acid are introduced into a second static mixer (7) for premixing, and then introduced into a mixing tank (8) for uniform mixing, and then introduced into a hot polymerization kettle (9) for copolymerization to obtain a copolymer intermediate, and the unreacted raw materials are returned to the second static mixer (7) through a bottom circulation pump of the hot polymerization kettle (9); Step 3: piperylene is introduced into the first static mixer (5), and is introduced into the third static mixer (10) with the DCPD obtained in step 1 through the first static mixer (5) and the batching tank (6) in sequence. At the same time, the copolymer intermediate obtained in step 2 is introduced into the third static mixer (10) and mixed with the DCPD uniformly, and then introduced into the polymerization kettle (11) for polymerization reaction to obtain a modified DCPD resin; Step 4: The modified DCPD resin is introduced into the reactor (13) through the raw material tank (12), and hydrogen is introduced into the reactor (13) at the same time. The reaction product is introduced into the coil heat exchanger (14) for heating and then enters the stripping tower (15) for stripping. At the same time, steam is introduced into the bottom of the stripping tower (15). The top product of the stripping tower (15) enters the first static mixer (5) for circulation through the oil-water separator (16), and a low-VOC bio-based modified DCPD hydrogenated resin is obtained in the bottom of the stripping tower (15).

2. The preparation process of the low VOC bio-based modified DCPD hydrogenated resin according to claim 1, characterized in that: The weight ratio of DCPD, vinyl cyclohexene, fumaric acid and / or itaconic acid is (70-90): (5-20): (5-15).

3. The preparation process of the low VOC bio-based modified DCPD hydrogenated resin according to claim 2, characterized in that: The copolymerization temperature is 180-220°C.

4. An application of the preparation process of the low VOC bio-based modified DCPD hydrogenated resin according to claim 2 or 3, characterized in that: The synthesized bio-based modified DCPD hydrogenated resin is used in one of pressure-sensitive adhesives or hot-melt adhesives.

5. The application of the preparation process of the low VOC bio-based modified DCPD hydrogenated resin according to claim 4, characterized in that: Calculated by weight percentage, the formula of the pressure-sensitive adhesive includes: 20-50% of SIS block copolymer, 10-30% of filler oil, and the balance is made up of low-VOC bio-based modified DCPD hydrogenated resin.

6. The application of the preparation process of the low VOC bio-based modified DCPD hydrogenated resin according to claim 4, characterized in that: Calculated by weight percentage, the formula of the hot melt adhesive includes: 20-50% of ethylene-vinyl acetate copolymer, 20-40% of lubricant, and low-VOC bio-based modified DCPD hydrogenated resin making up the balance.

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