Tear-resistant bio-based resin with low heating loss as well as preparation method and application of tear-resistant bio-based resin

Abstract

The invention discloses tear-resistant bio-based resin with low heating loss as well as a preparation method and application of the tear-resistant bio-based resin, and belongs to the technical field of resin. The preparation method of the resin comprises the following steps: carrying out polymerization reaction on cyclopentadiene and derivatives thereof and a bio-based olefin monomer in the presence of a first solvent, and then adding alpha-olefin for continuous reaction to obtain a polymerization solution A; carrying out flash evaporation on the polymer liquid A to obtain a bio-based cycloolefin copolymer B; removing impurities from the bio-based cycloolefin copolymer B in the presence of a second solvent, and then reacting the bio-based cycloolefin copolymer B with bio-based carboxylic acid and a peroxide initiator to obtain a polymer solution C; and mixing the polymer solution C with organic alcohol and a surfactant, and removing unreacted monomers, an initiator decomposition product, an unreacted solvent and oligomers to obtain the tear-resistant bio-based resin. The resin prepared by the method has the advantages of low heating loss and strong tear resistance, has good dynamic performance and higher modulus at a lower acid value, and has better weather resistance than a traditional product.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of resin, in particular to a tear-resistant bio-based resin with low heating loss and a preparation method and application thereof. BACKGROUND

[0002] The bio-based resin refers to a polymer material prepared by polymerization or modification through chemical and biological processes, taking renewable biomass resources as raw materials.

[0003] In the prior art, the bio-based resin applied in the field of tires mainly focuses on its tear resistance. The tear resistance of the resin directly determines the damage resistance of the tire rubber, and further affects the service life, driving safety and application scene adaptability of the tire. Although the bio-based resin prepared by the existing method has a certain tear resistance, it is limited in actual application due to the high heating loss. At present, there is no bio-based resin with better tear resistance and lower heating loss.

[0004] In view of this, the present application is proposed. SUMMARY

[0005] The present application aims to provide a tear-resistant bio-based resin with low heating loss and a preparation method and application thereof, so as to solve or improve the above technical problems.

[0006] The present application can be realized as follows: In a first aspect, the present application provides a preparation method of a tear-resistant bio-based resin with low heating loss, comprising the following steps: polymerizing cyclopentadiene and its derivatives with bio-based olefin monomers in the presence of a first solvent, and then adding an alpha-olefin for continuous reaction to obtain a polymerization liquid A; flash evaporating the polymerization liquid A to remove the first solvent and unreacted monomers, to obtain a bio-based cycloolefin copolymer B; removing impurities from the bio-based cycloolefin copolymer B in the presence of a second solvent through a filler bed loaded with gamma-alumina and activated clay, and then reacting with bio-based carboxylic acid and peroxide initiator to obtain a polymerization liquid C; mixing the polymerization liquid C with organic alcohol and surfactant, removing unreacted monomers and initiator decomposition products, and then removing unreacted solvents and oligomers through steam stripping to obtain a tear-resistant bio-based resin.

[0007] In an optional embodiment, the preparation of the polymerization liquid A comprises at least one of the following features: Feature 1: the mass ratio of cyclopentadiene and its derivatives to bio-based olefin monomers is 1:0.5 to 1:2; Feature 2: The cyclopentadiene and derivatives thereof include at least one of cyclopentadiene, methylcyclopentadiene, dimethylcyclopentadiene, dicyclopentadiene, methylcyclopentadiene dimer, and cyclopentadiene-methylcyclopentadiene dimer; Feature 3: The bio-based olefin monomer includes at least one of a-pinene, g-pinene, a-phellandrene, b-phellandrene, 2-carene, 3-carene, myrcene, dihydromyrcene, allo-ocimene, and (E)-B-ocimene; Feature 4: The a-olefin includes at least one of 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 1-heptene, and 1-octene; Feature 5: The mass of the first solvent is 20% to 90% of the total mass of the cyclopentadiene and derivatives thereof and the bio-based olefin monomer; Feature 6: The first solvent includes at least one of decalin and indane; Feature 7: The polymerization reaction is performed at 100°C to 280°C, 0.15 MPa to 3 MPa for 0.5 h to 6 h; Feature 8: The mass of the a-olefin is 0.5% to 10% of the mass of the cyclopentadiene and derivatives thereof; Feature 9: The reaction is continued for 0.25 h to 2 h after the a-olefin is added.

[0008] In an optional embodiment, the flashing of the polymerization liquid A is performed at 20 kPa to 80 kPa, 180°C to 250°C.

[0009] In an optional embodiment, the preparation of the polymerization liquid C includes at least one of the following features: Feature 10: The mass ratio of the bio-based cyclic olefin copolymer B to the second solvent is 1:0.5 to 1:9; Feature 11: The second solvent includes at least one of cyclohexane, methylcyclohexane, and dimethylcyclohexane; Feature 12: In the filler bed, the volume ratio of the g-alumina to the activated clay is 1:0.5 to 1:4; Feature 13: The bio-based carboxylic acid includes at least one of abietic acid, itaconic acid, hexyl itaconic acid, aconitic acid, ricinoleic acid, allyl succinic anhydride, 2-octenyl succinic anhydride, dodecenyl succinic anhydride, and 2,5-furandicarboxylic acid; Feature 14: The mass ratio of the bio-based carboxylic acid to the bio-based cyclic olefin copolymer B is 1:1 to 1:33; Feature 15: The peroxide initiator includes at least one of dibenzoyl peroxide, dicumyl peroxide, and di-t-butyl peroxide; Feature 16: The amount of the peroxide initiator added is 0.05% to 0.8% of the total mass of the bio-based cyclic olefin copolymer B and the bio-based carboxylic acid. Feature 17: After adding the bio-based carboxylic acid and the peroxide initiator, reacting at 60℃ to 95℃ for 5min to 30min.

[0010] In an alternative embodiment, the preparation of the tear-resistant bio-based resin comprises at least one of the following features: Feature 18: The mass ratio of the polymerization solution C to the organic alcohol is 1:0.05 to 1:0.50; Feature 19: The organic alcohol comprises at least one of methanol, ethanol, and propanol; Feature 20: The amount of the surfactant is 0.1% to 2.0% of the mass of the polymerization solution C; Feature 21: The surfactant comprises at least one of Span-60, Span-80, and Span-85; Feature 22: The steam stripping is performed at 0.2MPa to 0.8MPa and 180℃ to 320℃.

[0011] In a second aspect, the present application provides a tear-resistant bio-based resin with low heating loss, which is prepared by the preparation method of any one of the preceding embodiments.

[0012] In an alternative embodiment, the tear-resistant bio-based resin with low heating loss has at least one of the following features: Feature 23: The softening point of the tear-resistant bio-based resin is 80℃ to 160℃; Feature 24: The Gardner color number of the tear-resistant bio-based resin is ≤8Ga#; Feature 25: The Gardner color number of the tear-resistant bio-based resin after heating at 180℃ for 5h is ≤10Ga#; Feature 26: The acid value of the tear-resistant bio-based resin is 5mg KOH / g to 350mg KOH / g; Feature 27: The iodine value of the tear-resistant bio-based resin is 10mg / g to 300mg / g; Feature 28: The heating loss of the tear-resistant bio-based resin corresponding to heating at 200℃ for 3h is ≤1.0%.

[0013] In a third aspect, the present application provides a rubber composition, which contains the tear-resistant bio-based resin with low heating loss of the preceding embodiments.

[0014] In a fourth aspect, the present application provides a rubber, which is obtained by vulcanization treatment of the rubber composition of the preceding embodiments.

[0015] In a fifth aspect, the present application provides an application of the tear-resistant bio-based resin with low heating loss of the foregoing embodiment, or the rubber composition of the foregoing embodiment, or the rubber of the foregoing embodiment in the preparation of automobile parts, packaging materials, or electronic devices.

[0016] The beneficial effects of the present application include: The method of the bio-based resin provided by the present application improves the tear resistance of the bio-based resin through the regulation of the molecular weight of the cyclic olefin copolymer and the modification of the polar group, and effectively reduces the heating loss of the bio-based resin through the regulation of the polymerization reaction and the optimization of the post-treatment process.

[0017] The bio-based resin prepared by the method has the advantages of low heating loss and strong tear resistance, has good dynamic performance and high modulus at a low acid value, and has better weather resistance than traditional products. DETAILED DESCRIPTION

[0018] In order to make the purpose, technical scheme and advantages of the embodiments of the present application clearer, the technical scheme in the embodiments of the present application will be described clearly and completely below. If specific conditions are not specified in the embodiments, they are carried out according to conventional conditions or the conditions recommended by the manufacturer. If the reagents or instruments used are not specified by the manufacturer, they are all conventional products that can be purchased on the market.

[0019] The bio-based resin with low heating loss and its preparation method and application provided by the present application will be described in detail below.

[0020] The inventors have found that the bio-based resin in the prior art has better tear resistance, but usually has high heating loss. On the one hand, volatile small molecule substances are easily generated during heating, which reduces the adhesion of the rubber compound and may cause the tire to be not firmly bonded between layers. On the other hand, if the weight loss is too much at a temperature, not only the high molecular structure of the resin itself is changed, but also defects such as bubbles and pores may occur in the rubber compound, which affects the strength and durability of the tire.

[0021] Based on this, the present application provides a preparation method of a tear-resistant bio-based resin with low heating loss, which comprises the following steps: S1: polymerizing cyclopentadiene and its derivatives with bio-based olefin monomers in the presence of a first solvent, and then adding an alpha-olefin to continue the reaction to obtain a polymerization liquid A; S2: flash evaporation of the polymerization liquid A to remove the first solvent and unreacted monomers to obtain a bio-based cyclic olefin copolymer B; S3: removal of impurities from the bio-based cyclic olefin copolymer B in the presence of a second solvent through a filler bed loaded with gamma-alumina and activated clay, and then reaction with bio-based carboxylic acid and peroxide initiator to obtain a polymerization liquid C; S4: mixing the polymerization liquid C with organic alcohol and surfactant, removing unreacted monomer and initiator decomposition product, and then removing unreacted solvent and oligomer through steam stripping to obtain the tear-resistant bio-based resin.

[0022] In the above polymerization reaction of the cyclic olefin copolymer, the cyclopentadiene and its derivatives and the bio-based olefin monomer are first converted into a cyclic molecule through Diels-Alder reaction, and then an appropriate amount of alpha-olefin is added as a molecular weight regulator during the reaction to reduce the generation of macromolecular gel substances in the polymerization reaction, thereby obtaining the bio-based cyclic olefin copolymer B with low relative average molecular weight and small heat reduction. By using the bio-based cyclic olefin copolymer B as a reaction intermediate, a grafting reaction is carried out with bio-based carboxylic acid in the presence of a second solvent and a peroxide initiator, so that the unsaturated double bonds in the cyclic olefin copolymer copolymerize with the bio-based carboxylic acid containing unsaturated groups, and appropriate polar groups are introduced into the molecule, thereby obtaining the polymerization liquid C. Then, the polymerization liquid C is mixed with organic alcohol and surfactant to remove unnecessary substances, which is conducive to improving the stability of the bio-based resin and reducing the heat reduction thereof.

[0023] The bio-based resin prepared by the above method has the advantages of low heat reduction and strong tear resistance, and has good dynamic performance and high modulus at a relatively low acid value, and the weather resistance is better than that of traditional products.

[0024] The above S1 step is described in detail as follows.

[0025] In the above S1 step, the mass ratio of cyclopentadiene and its derivatives to bio-based olefin monomer can be 1:0.5 to 1:2, such as 1:0.5, 1:1, 1:1.5 or 1:2, etc., and can also be other values within the range of 1:0.5 to 1:2.

[0026] The cyclopentadiene and its derivatives can exemplarily include at least one of cyclopentadiene, methylcyclopentadiene, dimethylcyclopentadiene, dicyclopentadiene, methylcyclopentadiene dimer, and cyclopentadiene-methylcyclopentadiene dimer.

[0027] The bio-based olefin monomer can exemplarily include at least one of alpha-terpinene, gamma-terpinene, alpha-phellandrene, beta-phellandrene, 2-carene, 3-carene, myrcene, dihydromyrcene, allo-ocimene, and (E)-B-ocimene. In some preferred embodiments, the bio-based olefin monomer includes at least one of alpha-terpinene, gamma-terpinene, alpha-phellandrene, and myrcene.

[0028] The mass of the first solvent can be 20% to 90% of the total mass of the cyclopentadiene and its derivatives and the bio-based olefin monomer, such as 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 90%, etc., and can also be other values within the range of 20% to 90%.

[0029] The first solvent may, for example, include at least one of decalin and indane.

[0030] The polymerization reaction may be performed at 100°C to 280°C (e.g., 100°C, 150°C, 200°C, 250°C, or 280°C), 0.15 MPa to 3 MPa (e.g., 0.15 MPa, 0.5 MPa, 1 MPa, 1.5 MPa, 2 MPa, 2.5 MPa, or 3 MPa), for 0.5 h to 6 h (e.g., 0.5 h, 1 h, 2 h, 4 h, or 6 h).

[0031] The mass of the α-olefin may be 0.5% to 10% of the mass of the cyclopentadiene and derivatives thereof (e.g., 0.5%, 1%, 2%, 5%, 8%, or 10%), or other values within the range of 0.5% to 10%.

[0032] The α-olefin may, for example, include at least one of 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 1-heptene, and 1-octene.

[0033] After the α-olefin is added, the reaction is continued for 0.25 h to 2 h (e.g., 0.25 h, 0.5 h, 1 h, 1.5 h, or 2 h), or other values within the range of 0.25 h to 2 h.

[0034] The above process may be performed in a high-pressure reactor with stirring and filled with a protective gas (e.g., nitrogen).

[0035] The above S2 step is described in detail as follows.

[0036] In the above S2 step, the flashing of the polymerization liquid A may be performed at 20 kPa to 80 kPa (e.g., 20 kPa, 40 kPa, 60 kPa, or 80 kPa), 180°C to 250°C (e.g., 180°C, 200°C, 220°C, or 250°C).

[0037] The above S3 step is described in detail as follows.

[0038] In the above S3 step, the mass ratio of the bio-based cycloolefin copolymer B to the second solvent may be 1:0.5 to 1:9 (e.g., 1:0.5, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, or 1:9), or other values within the range of 1:0.5 to 1:9.

[0039] The second solvent may, for example, include at least one of cyclohexane, methylcyclohexane, and dimethylcyclohexane.

[0040] The volume ratio of the γ-alumina and the activated clay in the filler bed can be 1:0.5 to 1:4, such as 1:0.5, 1:1, 1:2, 1:3, or 1:4, or other values within the range of 1:0.5 to 1:4. In some preferred embodiments, the volume ratio of the γ-alumina and the activated clay is 1:1 to 1:2, which helps to obtain a product with better color number and less low-molecular impurities.

[0041] It should be noted that by loading the γ-alumina and the activated clay in the filler bed, the present application can effectively reduce the content of gel and low-molecular volatile substances (volatile components during resin heating), thereby facilitating the reduction of heating weight loss. If γ-alumina and diatomite are used as fillers, they are less effective than γ-alumina and activated clay in reducing the content of gel and low-molecular volatile substances.

[0042] The mass ratio of the bio-based carboxylic acid to the bio-based cycloolefin copolymer B can be 1:1 to 1:33, such as 1:1, 1:5, 1:10, 1:15, 1:20, 1:25, 1:30, or 1:33, or other values within the range of 1:1 to 1:33. In some preferred embodiments, the mass ratio of the bio-based carboxylic acid to the bio-based cycloolefin copolymer B is 1:2.86 to 1:10.

[0043] The bio-based carboxylic acid can exemplarily include at least one of abietic acid, itaconic acid, hexyl itaconic acid, aconitic acid, ricinoleic acid, allyl succinic anhydride, 2-octenyl succinic anhydride, dodecenyl succinic anhydride, and 2,5-furandicarboxylic acid. In some preferred embodiments, the bio-based carboxylic acid includes at least one of abietic acid and aconitic acid.

[0044] The amount of the peroxide initiator added can be 0.05% to 0.8% of the total mass of the bio-based cycloolefin copolymer B and the bio-based carboxylic acid, such as 0.05%, 0.1%, 0.2%, 0.4%, 0.6%, or 0.8%, or other values within the range of 0.05% to 0.8%. In some preferred embodiments, the amount of the peroxide initiator added can be 0.15% to 0.3% of the total mass of the bio-based cycloolefin copolymer B and the bio-based carboxylic acid.

[0045] The peroxide initiator can exemplarily include at least one of dibenzoyl peroxide, dicumyl peroxide, and di-t-butyl peroxide.

[0046] After the bio-based carboxylic acid and the peroxide initiator are added, the reaction can be carried out at 60°C to 95°C (such as 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, or 95°C) for 5 min to 30 min (such as 5 min, 10 min, 15 min, 20 min, 25 min, or 30 min).

[0047] Similarly, the above process can also be carried out in a high-pressure reactor with stirring and filled with a protective gas (such as nitrogen or the like).

[0048] The above S4 step is described in detail as follows. The above S1 step is described in detail as follows. The above S2 step is described in detail as follows. The above S3 step is described in detail as follows. The above S4 step is described in detail as follows.

[0049] In the above S4 step, the mass ratio of the polymerization solution C to the organic alcohol can be 1:0.05 to 1:0.50, such as 1:0.05, 1:0.1, 1:0.2, 1:0.3, 1:0.4, or 1:0.5, or the like, and can also be other values within the range of 1:0.05 to 1:0.50.

[0050] The organic alcohol can exemplarily include at least one of methanol, ethanol, and propanol.

[0051] The amount of the surfactant can be 0.1% to 2.0% of the mass of the polymerization solution C, such as 0.1%, 0.5%, 1%, 1.5%, or 2%, or the like, and can also be other values within the range of 0.1% to 2.0%. In some preferable embodiments, the amount of the surfactant is 0.15% to 0.5% of the mass of the polymerization solution C.

[0052] The surfactant can exemplarily include at least one of Span-60, Span-80, and Span-85.

[0053] The mixing of the polymerization solution C with the organic alcohol and the surfactant can be performed by a homogenizing circulation emulsifier, and then the mixture is allowed to stand, separated, and removed of unreacted monomers and initiator decomposition products. In this process, the organic alcohol functions as an absorbent, and the surfactant functions as a micellar aggregation for regulating the phase interface. By using an appropriate amount of the surfactant, the color number, the free acid value, and the low-molecular impurities can be reduced, the stability of the bio-based resin can be improved, and the heating loss of the bio-based resin can be reduced.

[0054] The steam stripping can be performed at a pressure of 0.2 MPa to 0.8 MPa (such as 0.2 MPa, 0.4 MPa, 0.6 MPa, or 0.8 MPa), and a temperature of 180°C to 320°C (such as 180°C, 200°C, 240°C, 280°C, 300°C, or 320°C).

[0055] Correspondingly, the application also provides a bio-based resin prepared by the above preparation method.

[0056] In some alternative embodiments, the bio-based resin has a softening point of 80°C to 160°C, such as 94.5°C to 120.6°C.

[0057] In some alternative embodiments, the bio-based resin has a Gardner color number of ≤8 Ga#, such as 3.2 Ga# to 6.0 Ga#.

[0058] In some alternative embodiments, the bio-based resin has a Gardner color number of ≤10 Ga# after heating at 180℃ for 5h, such as 4.0 Ga#-7.7 Ga#.

[0059] In some alternative embodiments, the bio-based resin has an acid value of 5 mg KOH / g-350 mg KOH / g, such as 14.6 mg KOH / g-226.8 mg KOH / g.

[0060] In some alternative embodiments, the bio-based resin has an iodine value of 10 mg / g-300 mg / g, such as 102 mg / g-162.5 mg / g.

[0061] In some alternative embodiments, the bio-based resin has a corresponding heating loss of ≤1.0% after heating at 200℃ for 3h, such as 0.37%-0.78%.

[0062] In addition, the present application also provides a rubber composition containing the bio-based resin described above.

[0063] Further, the rubber composition can further include cis-butadiene rubber, carbon black, zinc oxide, stearic acid, sulfur, and auxiliaries (such as anti-aging agents, accelerators, and anti-scorching agents, etc.).

[0064] Correspondingly, the present application also provides a rubber obtained by vulcanization of the rubber composition described above.

[0065] In addition, the present application also provides the use of the bio-based resin, the rubber composition, and the rubber described above, for example, in the preparation of automobile spare parts (such as rubber tires, automobile interior decoration, or automobile anti-damping spare parts, etc.), packaging materials, or electronic devices, etc.

[0066] The features and properties of the present application are further described in detail below in combination with examples.

[0067] The performance test methods of the resin herein include: The softening point, the Gardner color number, and the thermal stability are tested according to GB / T 24138 "Petroleum Resin"; the acid value is tested according to International Standard ISO 2554 "Plastics - Unsaturated polyester resins - Determination of hydroxyl value"; and the iodine value is tested according to GB / T 1676 "Determination of Iodine Value of Plasticizers".

[0068] Heating loss test method: 25g ± 0.1g of sample was weighed in a constant weight treated 100mL beaker, the beaker was placed in a tray and then placed in a constant temperature drying oven with a temperature of 200℃ ± 2℃, the air blowing function was turned on, after heating for 5h ± 5min, the beaker was taken out, placed in a desiccator containing desiccant color-changing silica gel for 30min, and then weighed after cooling. The percentage of the mass loss of the resin after heating to the mass of the original sample was taken as the heating loss of the sample.

[0069] Example 1 The present embodiment provides a low-heat-loss tear-resistant bio-based resin, and a preparation method thereof, which comprises: S1: A first solvent was pre-added in a high-pressure reaction kettle with stirring and nitrogen protection, then a mixture of cyclopentadiene and a bio-based olefin monomer was added into the high-pressure reaction kettle for polymerization, and then an α-olefin was added for further reaction to obtain a polymerization liquid A.

[0070] In the embodiment, the first solvent is indane, the bio-based olefin monomer is α-phellandrene, and the α-olefin is 3-methyl-1-pentene. The mass of the first solvent is 70% of the total mass of cyclopentadiene and the bio-based olefin monomer, the mass ratio of cyclopentadiene to the bio-based olefin monomer is 1:0.8, and the mass of the α-olefin is 5% of the mass of cyclopentadiene. The polymerization was carried out at 200℃ and 0.3MPa for 4h, and after the addition of the α-olefin, the reaction was continued at 220℃ and 0.32MPa for 0.5h.

[0071] S2: The polymerization liquid A was subjected to flash evaporation to remove the first solvent and unreacted monomers to obtain a bio-based cycloolefin copolymer B.

[0072] In the embodiment, the flash evaporation was carried out at 40kPa and 235℃.

[0073] S3: The bio-based cycloolefin copolymer B was mixed with a second solvent, then passed through a filler bed loaded with γ-alumina and activated clay, filtered to remove impurities, and then sent to a reaction kettle with stirring and nitrogen protection; then a bio-based carboxylic acid and a peroxide initiator were added for reaction to obtain a polymerization liquid C.

[0074] In the embodiment, the second solvent is methylcyclohexane, the bio-based carboxylic acid is abietic acid, and the peroxide initiator is dibenzoyl peroxide. The mass ratio of the bio-based cycloolefin copolymer B to the second solvent is 1:4; in the filler bed, the volume ratio of γ-alumina to activated clay is 1:1; the mass ratio of the bio-based carboxylic acid to the bio-based cycloolefin copolymer B is 1:10; and the amount of the peroxide initiator added is 0.3% of the total mass of the bio-based cycloolefin copolymer B and the bio-based carboxylic acid. After the addition of the bio-based carboxylic acid and the peroxide initiator, the reaction was carried out at 75℃ for 15min.

[0075] S4: mixing the polymerization liquid C with organic alcohol, then adding surfactant, mixing well by homogenizing circulating emulsifier, sending into buffer tank for standing for 40 min, removing unreacted monomer and initiator decomposition product, separating the obtained polymerization liquid phase into steam stripping device to remove unreacted solvent and oligomer, and obtaining the tear-resistant bio-based resin.

[0076] The organic alcohol is ethanol, and the surfactant is Span-80; the mass ratio of the polymerization liquid C to the organic alcohol is 1:0.3; and the amount of the surfactant is 0.15% of the mass of the polymerization liquid C. The steam stripping is performed at 0.5 MPa and 270 DEG C.

[0077] Example 2 The present embodiment provides a tear-resistant bio-based resin with low heating loss, and a preparation method thereof. S1: in a high-pressure reaction kettle with stirring and nitrogen protection, a first solvent is pre-added, then a biological alkene monomer is added into the high-pressure reaction kettle for polymerization reaction, and then an alpha-olefin is added for continuous reaction, to obtain a polymerization liquid A.

[0078] The first solvent is indane, the biological alkene monomer is alpha-octalone, and the alpha-olefin is 3-methyl-1-pentene. The mass of the first solvent is 20% of the total mass of the cyclopentadiene and the biological alkene monomer, the mass ratio of the cyclopentadiene to the biological alkene monomer is 1:0.5, and the mass of the alpha-olefin is 0.5% of the mass of the cyclopentadiene. The polymerization reaction is performed at 100 DEG C and 0.15 MPa for 0.5 h, and then the alpha-olefin is added for continuous reaction at 120 DEG C and 0.20 MPa for 0.25 h.

[0079] S2: the polymerization liquid A is subjected to flash evaporation to remove the first solvent and unreacted monomer, to obtain a biological cycloalkene copolymer B.

[0080] The flash evaporation is performed at 20 kPa and 180 DEG C.

[0081] S3: the biological cycloalkene copolymer B is mixed with a second solvent, then filtered through a filler bed loaded with gamma-alumina and activated clay to remove impurities, and then sent into a reaction kettle with stirring and nitrogen protection; then a biological carboxylic acid and a peroxide initiator are added for reaction, to obtain a polymerization liquid C.

[0082] The second solvent is methylcyclohexane, the bio-based carboxylic acid is abietic acid, and the peroxide initiator is dibenzoyl peroxide. The mass ratio of the bio-based cycloalkene copolymer B to the second solvent is 1:0.5; in the filler bed, the volume ratio of γ-alumina to activated clay is 1:0.5; the mass ratio of the bio-based carboxylic acid to the bio-based cycloalkene copolymer B is 1:1; and the amount of the peroxide initiator added is 0.05% of the total mass of the bio-based cycloalkene copolymer B and the bio-based carboxylic acid. After the bio-based carboxylic acid and the peroxide initiator are added, the reaction is carried out at 60°C for 5 minutes.

[0083] S4: The above polymerization liquid C is mixed with an organic alcohol, a surfactant is added, and the mixture is fully mixed by a homogenizing circulating emulsifier, then is sent into a buffer tank for standing for 40 minutes to remove unreacted monomers and initiator decomposition products, and the obtained polymerization liquid phase is separated and sent into a steam stripping device to remove unreacted solvents and oligomers, thereby obtaining a tear-resistant bio-based resin.

[0084] The organic alcohol is ethanol, and the surfactant is Span-80; the mass ratio of the polymerization liquid C to the organic alcohol is 1:0.05; and the amount of the surfactant is 0.1% of the mass of the polymerization liquid C. The steam stripping is carried out at 0.2 MPa and 180°C.

[0085] Example 3 The present embodiment provides a tear-resistant bio-based resin with low heating loss, and a preparation method thereof. S1: A first solvent is pre-added into a high-pressure reaction kettle with stirring and nitrogen protection, then a cyclopentadiene and a bio-based olefin monomer are fully mixed and added into the high-pressure reaction kettle for polymerization reaction, and then an α-olefin is added for continuous reaction, thereby obtaining a polymerization liquid A.

[0086] The first solvent is decalin, the bio-based olefin monomer is α-ostrutholene, and the α-olefin is 3-methyl-1-pentene. The mass of the first solvent is 90% of the total mass of the cyclopentadiene and the bio-based olefin monomer, the mass ratio of the cyclopentadiene to the bio-based olefin monomer is 1:2, and the mass of the α-olefin is 10% of the mass of the cyclopentadiene. The polymerization reaction is carried out at 275°C and 2.8 MPa for 6 hours, and then the α-olefin is added for continuous reaction at 280°C and 2.9 MPa for 2 hours.

[0087] S2: The above polymerization liquid A is subjected to flash evaporation to remove the first solvent and unreacted monomers, thereby obtaining a bio-based cycloalkene copolymer B.

[0088] The flash evaporation is carried out at 80 kPa and 250°C.

[0089] S3: The above bio-based cycloolefin copolymer B is mixed with a second solvent, then passed through a filler bed loaded with γ-alumina and activated clay, filtered to remove impurities, and then fed into a reaction kettle with stirring and nitrogen protection; then bio-based carboxylic acid and peroxide initiator are added for reaction to obtain polymerization liquid C.

[0090] The second solvent is methylcyclohexane, the bio-based carboxylic acid is abietic acid, and the peroxide initiator is dibenzoyl peroxide. The mass ratio of bio-based cycloolefin copolymer B to the second solvent is 1:9; in the filler bed, the volume ratio of γ-alumina to activated clay is 1:4; the mass ratio of bio-based carboxylic acid to bio-based cycloolefin copolymer B is 1:33; and the amount of peroxide initiator added is 0.8% of the total mass of bio-based cycloolefin copolymer B and bio-based carboxylic acid. After adding bio-based carboxylic acid and peroxide initiator, the reaction is carried out at 95°C for 30 min.

[0091] S4: The above polymerization liquid C is mixed with an organic alcohol, and a surfactant is added, then fully mixed by a homogenizing circulating emulsifier, fed into a buffer tank for 40 min of standing, to remove unreacted monomers and initiator decomposition products, and the obtained polymerization liquid phase is separated and fed into a steam stripping device to remove unreacted solvents and oligomers, to obtain a tear-resistant bio-based resin.

[0092] The organic alcohol is ethanol, and the surfactant is Span-85; the mass ratio of polymerization liquid C to organic alcohol is 1:0.5; and the amount of surfactant used is 2% of the mass of polymerization liquid C. Steam stripping is carried out at 0.5 MPa and 270°C.

[0093] Example 4 The difference between this example and Example 1 is that in S3, the mass ratio of bio-based carboxylic acid to bio-based cycloolefin copolymer B is 1:4.

[0094] Example 5 The difference between this example and Example 1 is that in S3, the mass ratio of bio-based carboxylic acid to bio-based cycloolefin copolymer B is 1:2.86.

[0095] Example 6 The difference between this example and Example 1 is that in S3, the bio-based carboxylic acid is aconitic acid, and the mass ratio of bio-based carboxylic acid to bio-based cycloolefin copolymer B is 1:2.86.

[0096] Example 7 The difference between this example and Example 1 is that in S3, the amount of peroxide initiator added is 0.15% of the total mass of bio-based cycloolefin copolymer B and bio-based carboxylic acid.

[0097] Comparative Example 1 This comparative example provides a bio-based resin, which is prepared by the following method: S1: In a high-pressure reactor with stirring and nitrogen protection, 40% of the total material by mass of indane was pre-added as the first solvent, and cyclopentadiene and norbornene were mixed in a mass ratio of 1:1 and then added to the high-pressure reactor. The thermal free radical polymerization was carried out at 175°C and 0.25 MPa for 2.0 h. Then 1.5% of the total material by mass of divinyl ether was added, and the reaction was continued at 200°C and 0.25 MPa for 8 h to obtain a first polymerization liquid.

[0098] S2: The first polymerization liquid was transported to a flash tower, and the first solvent and unreacted monomers were removed at a pressure of 40 kPa and a temperature of 235°C. The light components obtained from the top of the flash tower were introduced into a microporous membrane separator, and the indane separated by the microporous membrane separator was reused in the reactor. The bottom of the flash tower obtained a cycloolefin copolymer with a Gardner color number of 2.0# and a melt viscosity (@ 40°C) of 1250 mPa·s.

[0099] S3: The cycloolefin copolymer was pre-transported into a packed tower (the packing was composed of γ-alumina and diatomite in a volume ratio of 1:0.3) to remove impurities, and then the cycloolefin copolymer was uniformly mixed with rosin acid and a second solvent (methylcyclohexane and benzene in a mass ratio of 1:1) in a mass ratio of 0.5:1:2, and then was sent into a fixed bed reactor loaded with a modified phosphotungstic acid catalyst (containing 30wt% of active component Cs 2.5 H 0.5 PW 12 O 40 , and the carrier was SBA-15) at 100°C and 0.12 MPa for 1.0 h to obtain a second polymerization liquid.

[0100] S4: The second polymerization liquid was introduced into an alcohol washing kettle, 20% of the second polymerization liquid by mass of methanol was added to wash off the unreacted monomers, and then was introduced into a rectifying tower to remove the second solvent and oligomers at a pressure of 40 kPa and a temperature of 250°C to obtain a tear-resistant bio-based resin.

[0101] The performance comparison results of the bio-based resins prepared in Examples 1-7 and Comparative Example 1 are shown in Table 1.

[0102] Table 1 Comparison results

[0103] Compared with Comparative Example 1, the product obtained in Example 1, Example 3-7 has lower heating loss, higher thermal stability, higher softening point, and lower iodine value, which indicates that the grafting reaction has higher conversion rate, and the carboxylic acid group content and saturation degree of the product are higher. At the same time, the above scheme optimizes the low molecular residue and impurity control process, so that the volatile components of the product are greatly reduced at high temperature, and the application effect in the composite material system is improved. In Example 6, aconitic acid is used as a bio-based carboxylic acid, and the aconitic acid molecule contains three carboxylic acid groups. The acid value of the obtained bio-based resin is about 3 times that of the bio-based resin obtained by using a bio-based carboxylic acid containing a single carboxylic acid group.

[0104] As can be seen from the above examples, with the increase of the carboxylic acid groups (corresponding to bio-based carboxylic acid) participating in the reaction (such as Example 1, Example 4-5), the softening point, color number and acid value of the product resin are correspondingly increased, and the iodine value is correspondingly reduced, which shows a good carboxylic acid grafting effect. In addition, the amount of initiator (such as Example 1 and Example 7) also has a more obvious effect on the product performance, which indicates that the amount of initiator will affect the grafting rate.

[0105] Example 8 The difference between this example and Example 1 is that the bio-based olefin monomer is γ-terpinene.

[0106] Example 9 The difference between this example and Example 1 is that the bio-based olefin monomer is 3-carene.

[0107] Example 10 The difference between this example and Example 1 is that the bio-based olefin monomer is myrcene.

[0108] Comparative Example 2 The difference between this comparative example and Example 1 is that no α-olefin is added in S1.

[0109] Specifically, the preparation process is as follows: a first solvent is pre-added in a high-pressure reaction kettle with stirring and nitrogen protection, then the cyclopentadiene and the bio-based olefin monomer are fully mixed and added into the high-pressure reaction kettle to perform a polymerization reaction at 200℃ and 0.30MPa, and after reacting for 4.0h, the reaction is continued at 220℃ and 0.32MPa for 0.5h to obtain a polymerization liquid A. The selection and amount of the materials are the same as in Example 1.

[0110] Comparative Example 3 The difference between this comparative example and Example 1 is that no bio-based olefin copolymer is added in S1.

[0111] Specifically, the preparation process is as follows: a first solvent is added in advance in a high-pressure reaction kettle with stirring and nitrogen protection, then cyclopentadiene is added, and a polymerization reaction is carried out at 200°C and 0.30 MPa, after 4.0 h of reaction, an α-olefin is added, and the reaction is continued at 220°C and 0.32 MPa for 0.5 h to obtain a first polymerization liquid. The selection and amount of the materials are the same as in Example 1.

[0112] The performance comparison results of the bio-based cycloolefin copolymers B and bio-based resins prepared in Examples 8-10 and Comparative Examples 2-3 are shown in Table 2.

[0113] Table 2 Influence of different comonomers on the performance of products

[0114] As can be seen from Table 2: As can be seen from Examples 1 and 8-9, α-phellandrene, γ-terpinene and 3-carene have similar molecular structures, and the cycloolefin copolymers and bio-based resins obtained by copolymerization of cyclopentadiene and 3-methyl-1-pentene have approximately the same physicochemical properties; while laurylene (Example 10) is a fatty chain-shaped olefin, the copolymer thereof has a smaller weight average molecular weight, a narrower average molecular weight distribution, a higher iodine value, and the bio-based resin obtained by carboxylic acid modification thereof can have a lower color number, a lower softening point and a heating loss, and a higher acid value, and has a more extensive application.

[0115] Comparative Example 2 is a copolymer of cyclopentadiene and α-phellandrene, and Comparative Example 3 is a copolymer of cyclopentadiene and 3-methyl-1-pentene, and the corresponding copolymers have a significantly increased melt viscosity, and the obtained resins have a significantly deteriorated color and heating loss.

[0116] Example 11 The difference between this example and Example 1 is that in S3, the volume ratio of γ-alumina to activated clay in the filler bed is 1:2.

[0117] Example 12 The difference between this example and Example 1 is that in S4, the organic alcohol is propanol, the surfactant is Span-60, and the amount of the surfactant is 0.5% of the mass of the polymerization liquid C.

[0118] Comparative Example 4 The difference between this comparative example and Example 1 is that in S3, the filler loaded in the filler bed is only γ-alumina.

[0119] Comparative Example 5 The difference between this comparative example and Example 1 is that in S3, the filler loaded in the filler bed is γ-alumina and diatomite with a volume ratio of 1:1.

[0120] Comparative Example 6 The difference between this comparative example and Example 1 is that no surfactant is added in S4.

[0121] Comparative Example 7 The difference between this comparative example and Example 1 is that the amount of surfactant used in S4 is 3% of the mass of the polymerization solution C.

[0122] The performance comparison results of the bio-based resins prepared in Examples 11-12 and Comparative Examples 4-7 are shown in Table 3.

[0123] Table 3 Influence of different post-treatment conditions on the performance of bio-based resins

[0124] As can be seen from Table 3: From Examples 1, 11 and Comparative Example 4, it can be seen that, in the S3 step, when the active clay proportion in the filler is appropriately increased before modification of the cycloolefin copolymer, it is helpful to obtain a product with better color number and less low-molecular impurities.

[0125] From Examples 1 and Comparative Example 5, it can be seen that, compared with the combination of γ-alumina and diatomite, the combination of γ-alumina and active clay in the same proportion is more conducive to obtaining a product with a higher softening point, a lighter color number and a lower heating loss.

[0126] From Examples 12, Comparative Example 6 and Comparative Example 7, it can be seen that, in the S4 step, the use of an appropriate amount of surfactant can reduce the color number, free acid value and low-molecular impurities, improve the stability of the bio-based resin, and reduce the heating loss of the bio-based resin, which plays a key role in the physical and chemical properties of the final product.

[0127] Application Example This application example provides five rubber composition samples, which are blank group, experimental groups 1-3 and control group, respectively. The formula of the rubber composition samples is shown in Table 4. Among them, the bio-based resins used in experimental groups 1-3 are respectively the bio-based resins prepared in Example 1, Example 5 and Example 10, and the bio-based resin used in the control group is the bio-based resin prepared in Comparative Example 1.

[0128] Table 4 Formula of rubber composition

[0129] Among them, “phr” means the mass fraction of additives per 100 parts of rubber.

[0130] The rubber compositions of each group are subjected to three-stage pre-vulcanization, and the vulcanization conditions are 153℃×25min, 153℃×35min and 153℃×50min.

[0131] The following performance tests were carried out after vulcanization treatment, and the determination conditions included: The tear strength was tested according to the method specified in GB / T 529 “Determination of tear strength of vulcanized rubber or thermoplastic rubber (pant, right angle and crescent shaped samples)”; the 300% modulus, 100% modulus, tensile strength, elongation at break were tested according to the method specified in GB / T 528 “Determination of tensile stress-strain properties of vulcanized rubber or thermoplastic rubber”; the hardness was tested according to the method specified in GB / T 6031; the Mooney viscosity ML (1+4) 100 ℃ was tested according to the method specified in GB / T 1232.1; and the Mooney scorch time was tested according to the method specified in GB / T 1233.

[0132] The determination results are shown in Tables 5 and 6.

[0133] Table 5 Physical properties of rubber compositions

[0134] Table 6 Mooney viscosity and Mooney scorch time

[0135] From Tables 5 and 6, it can be seen that the rubber compositions in experimental groups 1-3 were sequentially added with 3 phr of the biomass-based resin prepared by the biomass-based resin of Example 1, Example 5 and Example 10 of the present application, and the tear strength and elongation at break of the rubber compositions before and after vulcanization were all significantly improved. At the same time, at the initial stage of vulcanization, the Mooney viscosity ML (1+4) 100 ℃ of the rubber composition after adding the biomass-based resin was generally smaller than that of the rubber composition without adding the biomass-based resin, and the Mooney scorch time (t 35- 5) was shortened, showing better processing performance.

[0136] The biomass-based resin used in the control group was a carboxylic acid modified resin obtained by using another polymerization process. Compared with the data of experimental group 2, it can be seen that, under the condition of similar acid value of the modified resin, the Mooney viscosity after aging was lower, the Mooney scorch time (t 35- 5) was relatively longer, and the comprehensive performance of the modified resin as a tear resistance modifier was relatively poor.

[0137] In summary, the biomass-based resin prepared by the present application has the advantages of low heating loss and strong tear resistance, and has good dynamic performance and high modulus at a low acid value, and the weather resistance is better than that of traditional products.

[0138] The above merely provides the preferred embodiments of the present application, and is not used to limit the present application. For those skilled in the art, the present application can have various modifications and changes. Any modifications, equivalent replacements, improvements, etc. made within the principles and technical scope of the present application shall fall into the scope of the present application.

Claims

1. A method for preparing a tear-resistant bio-based resin with low heat loss, characterized in that, Includes the following steps: Cyclopentadiene and its derivatives were polymerized with bio-based olefin monomers in the presence of a first solvent, followed by the addition of α-olefins to continue the reaction, yielding polymer solution A. The polymerization liquid A is flash evaporated to remove the first solvent and unreacted monomers to obtain bio-based cyclic olefin copolymer B; The bio-based cyclic olefin copolymer B, in the presence of a second solvent, is impurity removed by passing through a packed bed loaded with γ-alumina and activated clay, and then reacted with a bio-based carboxylic acid and a peroxide initiator to obtain a polymerization solution C; The polymerization liquid C is mixed with organic alcohol and surfactant to remove unreacted monomers and initiator decomposition products. Then, unreacted solvents and oligomers are removed by steam stripping to obtain tear-resistant bio-based resin.

2. The preparation method according to claim 1, characterized in that, The preparation of the polymerization liquid A includes at least one of the following characteristics: Feature 1: The mass ratio of the cyclopentadiene and its derivatives to the bio-based olefin monomer is 1:0.5 to 1:2; Feature 2: The cyclopentadiene and its derivatives include at least one of cyclopentadiene, methylcyclopentadiene, dimethylcyclopentadiene, dicyclopentadiene, methylcyclopentadiene dimer and cyclopentadiene-methylcyclopentadiene dimer; Feature 3: The bio-based olefin monomer includes at least one of α-terpinene, γ-terpinene, α-phellandrene, β-phellandrene, 2-carene, 3-carene, myrcene, dihydromyrcene, allocimenene, and (E)-B-ocimene; Feature 4: The α-olefin includes at least one selected from 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 1-heptene, and 1-octene; Feature 5: The mass of the first solvent is 20% to 90% of the total mass of the cyclopentadiene and its derivatives and the bio-based olefin monomer; Feature 6: The first solvent comprises at least one of decahydronaphthalene and indene; Feature 7: The polymerization reaction is carried out at 100℃~280℃ and 0.15MPa~3MPa for 0.5h~6h; Feature 8: The mass of the α-olefin is 0.5% to 10% of the mass of the cyclopentadiene and its derivatives; Feature 9: After adding the α-olefin, continue the reaction for 0.25 h to 2 h.

3. The preparation method according to claim 1, characterized in that, The flash evaporation of the polymerization liquid A is carried out under conditions of 20 kPa~80 kPa and 180℃~250℃.

4. The preparation method according to claim 1, characterized in that, The preparation of the polymerization liquid C includes at least one of the following characteristics: Feature 10: The mass ratio of the bio-based cyclic olefin copolymer B to the second solvent is 1:0.5 to 1:9; Feature 11: The second solvent comprises at least one of cyclohexane, methylcyclohexane, and dimethylcyclohexane; Feature 12: In the packed bed, the volume ratio of the γ-alumina to the activated clay is 1:0.5 to 1:4; Feature 13: The bio-based carboxylic acid includes at least one of rosin acid, itaconic acid, hexyl itaconic acid, aconitic acid, ricinoleic acid, allyl succinic anhydride, 2-octenyl succinic anhydride, dodecenyl succinic anhydride and 2,5-furandicarboxylic acid. Feature 14: The mass ratio of the bio-based carboxylic acid to the bio-based cyclic olefin copolymer B is 1:1 to 1:33; Feature 15: The peroxide initiator includes at least one of benzoyl peroxide, dicumyl peroxide, and ditert-butyl peroxide; Feature 16: The amount of the peroxide initiator added is 0.05% to 0.8% of the total mass of the bio-based cyclic olefin copolymer B and the bio-based carboxylic acid; Feature 17: After adding the bio-based carboxylic acid and the peroxide initiator, the reaction is carried out at 60℃~95℃ for 5min~30min.

5. The preparation method according to claim 1, characterized in that, The preparation of the tear-resistant bio-based resin includes at least one of the following characteristics: Feature 18: The mass ratio of the polymerization liquid C to the organic alcohol is 1:0.05 to 1:0.50; Feature 19: The organic alcohol comprises at least one of methanol, ethanol, and propanol; Feature 20: The amount of surfactant used is 0.1% to 2.0% of the mass of the polymerization liquid C; Feature 21: The surfactant includes at least one of Span-60, Span-80, and Span-85; Feature 22: Steam stripping is carried out under conditions of 0.2MPa~0.8MPa and 180℃~320℃.

6. A tear-resistant bio-based resin with low heat loss, characterized in that, It is prepared by the preparation method according to any one of claims 1 to 5.

7. The low-heat-loss, tear-resistant bio-based resin according to claim 6, characterized in that, The tear-resistant bio-based resin has at least one of the following characteristics: Feature 23: The softening point of the tear-resistant bio-based resin is 80℃~160℃; Feature 24: The Gardner color number of the tear-resistant bio-based resin is ≤8Ga#; Feature 25: The Gardner color number of the tear-resistant bio-based resin after heating at 180°C for 5 hours is ≤10Ga#; Feature 26: The acid value of the tear-resistant bio-based resin is 5 mg KOH / g to 350 mg KOH / g; Feature 27: The iodine value of the tear-resistant bio-based resin is 10 mg / g to 300 mg / g; Feature 28: The tear-resistant bio-based resin has a heat loss of ≤1.0% after heating at 200°C for 3 hours.

8. A rubber composition, characterized in that, The rubber composition contains the low-heat-shrinkage, tear-resistant bio-based resin as described in claim 6 or 7.

9. A type of rubber, characterized in that, The rubber is obtained by vulcanization of the rubber composition of claim 8.

10. The use of a low-heat-shrinkage, tear-resistant bio-based resin as described in any one of claims 6-7, or the rubber composition as described in claim 8, or the rubber as described in claim 9, in the preparation of automotive parts, packaging materials, or electronic devices.

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