CN110483848B - Application of lignin-unsaturated carboxylate composite reinforcing agent in rubber - Google Patents
Application of lignin-unsaturated carboxylate composite reinforcing agent in rubber Download PDFInfo
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- CN110483848B CN110483848B CN201910778054.3A CN201910778054A CN110483848B CN 110483848 B CN110483848 B CN 110483848B CN 201910778054 A CN201910778054 A CN 201910778054A CN 110483848 B CN110483848 B CN 110483848B
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- 229920003052 natural elastomer Polymers 0.000 claims description 14
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 14
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 14
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- 238000000034 method Methods 0.000 claims description 13
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- 238000002360 preparation method Methods 0.000 claims description 3
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011121 hardwood Substances 0.000 claims description 2
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- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 2
- 229960002447 thiram Drugs 0.000 claims description 2
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- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 239000004636 vulcanized rubber Substances 0.000 abstract description 3
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- DZBOAIYHPIPCBP-UHFFFAOYSA-L magnesium;2-methylprop-2-enoate Chemical compound [Mg+2].CC(=C)C([O-])=O.CC(=C)C([O-])=O DZBOAIYHPIPCBP-UHFFFAOYSA-L 0.000 description 2
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- CCNDOQHYOIISTA-UHFFFAOYSA-N 1,2-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1C(C)(C)OOC(C)(C)C CCNDOQHYOIISTA-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
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- OAKHANKSRIPFCE-UHFFFAOYSA-L calcium;2-methylprop-2-enoate Chemical compound [Ca+2].CC(=C)C([O-])=O.CC(=C)C([O-])=O OAKHANKSRIPFCE-UHFFFAOYSA-L 0.000 description 1
- TXTCTCUXLQYGLA-UHFFFAOYSA-L calcium;prop-2-enoate Chemical compound [Ca+2].[O-]C(=O)C=C.[O-]C(=O)C=C TXTCTCUXLQYGLA-UHFFFAOYSA-L 0.000 description 1
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- DWLAVVBOGOXHNH-UHFFFAOYSA-L magnesium;prop-2-enoate Chemical compound [Mg+2].[O-]C(=O)C=C.[O-]C(=O)C=C DWLAVVBOGOXHNH-UHFFFAOYSA-L 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a lignin-unsaturated carboxylate composite reinforcing agent and application thereof in rubber. Compared with the prior art, the high-performance rubber reinforcing agent is prepared by adopting a lignin and unsaturated carboxylate reactive grinding mode, the metal ions in the unsaturated carboxylate and the polar functional groups in the lignin structure are utilized to generate chelation, the dispersion of the lignin is facilitated, meanwhile, the unsaturated carboxylate can generate self-polymerization and grafting reaction with a rubber matrix in the vulcanization process to form an ion crosslinking chemical bond, the mechanical properties of the vulcanized rubber are obviously improved, and the high-performance rubber reinforcing agent has wide market application prospect.
Description
Technical Field
The invention belongs to the technical field of reinforcing superfine powder and the technical field of rubber composite materials, and particularly relates to a lignin-unsaturated carboxylate composite reinforcing agent and application thereof in rubber.
Background
Lignin is the second largest biomass resource in the world next to cellulose, but is used as a waste in the biorefinery industry and the paper industry for a long time, so that the recycling rate is low, and serious environmental pollution is caused. Lignin has a highly crosslinked molecular structure and excellent aging resistance and thermal stability, and is expected to be applied to the rubber field as a high-performance reinforcing agent, but has strict requirements on the particle size. The lignin structure contains a large amount of phenolic hydroxyl groups, so that the intermolecular force is large, the lignin is easy to agglomerate into large particles, and the lignin is difficult to disperse and is not beneficial to reinforcing rubber.
In the field of rubber processing, the particle size has a decisive influence on the reinforcing effect of the rubber matrix, and particles with large particle sizes only play a role of a filler. Therefore, there is a need to develop new process technologies to improve the dispersion of lignin in rubber.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to solve the technical problem of providing a lignin-unsaturated carboxylate composite reinforcing agent aiming at the defects of the prior art.
The invention also provides the application of the lignin-unsaturated carboxylate composite reinforcing agent in rubber.
In order to solve the technical problem, the invention discloses a preparation method of a lignin-unsaturated carboxylate composite reinforcing agent, which comprises the following steps: adding lignin and unsaturated carboxylate into grinding equipment, and adjusting the process until the material meets the required particle size.
Wherein the lignin is any one or combination of more of herbaceous lignin, hardwood lignin, softwood lignin and lignin modified by the lignin; wherein, the modification is any one or combination of acylation, esterification, etherification, phenolization, alkylation and demethylation modification.
The unsaturated carboxylate is any one or combination of more of zinc methacrylate, magnesium methacrylate, calcium methacrylate, zinc acrylate, magnesium acrylate and calcium acrylate, can perform self-polymerization and grafting reaction with a rubber matrix in the vulcanization process, and overcomes the problems that the polyacrylate does not have self-polymerization capability because of being a polymer and is difficult to graft or crosslink with the rubber matrix; the mass part ratio of the lignin to the unsaturated carboxylate is (1-25) to (1-15).
The unsaturated carboxylate serving as a common rubber processing aid can be subjected to copolymerization and grafting reaction with a rubber matrix in the vulcanization process to form an ionic crosslinking bond, so that various mechanical properties of vulcanized rubber are remarkably improved. According to the invention, lignin and unsaturated carboxylate are subjected to reactive grinding, and the lignin-unsaturated carboxylate composite reinforcing agent is obtained through ionic interaction, so that the dispersibility of lignin in rubber can be further improved, and the reinforced rubber with excellent performance can be obtained.
Wherein, the grinding equipment is a ball millAny one of an ultrafine grinder and a jet mill; the particle size is d50Less than 20 μm, d90Less than 50 μm.
Wherein, the grinding device is preferably a jet mill and an ultrafine mill, and more preferably a jet mill.
The specific process of adopting the jet mill comprises the steps of mixing and stirring lignin and unsaturated carboxylate uniformly, injecting the mixture into the jet mill, introducing 0.5-1.0 MPa of compressed air, crushing the material by high-pressure airflow, adding the crushed material into a classifier or a classifying chamber for classification, wherein the rotating speed of the classifier is 6000-10000 rpm/min, returning the classified material with the mesh number of more than or equal to 3000 to the jet mill for re-crushing, and discharging the classified material with the mesh number of less than 3000 from a discharge port to obtain the lignin-unsaturated carboxylate composite reinforcing agent with the mesh number of less than 3000.
The method comprises the specific process of adopting the ultrafine pulverizer, wherein the specific process comprises the steps of mixing and stirring lignin and unsaturated carboxylate uniformly, adding the mixture into a hopper of the ultrafine pulverizer, adjusting the distance between grinding discs to be 2-5 mu m, rotating at 1000-2000 rpm/min, and circulating for 2-5 times to fully grind the materials to obtain the lignin-unsaturated carboxylate composite reinforcing agent.
The specific process of adopting the ball mill comprises the steps of adding lignin and unsaturated carboxylate into a ball milling tank, adding 20 big balls and 50 small balls, rotating the ball mill at 300-600 rpm/min, alternately operating forward and reverse directions for 3-6 times, discharging after 2 hours each time for 30min, and obtaining the lignin-unsaturated carboxylate composite reinforcing agent.
The lignin-unsaturated carboxylate composite reinforcing agent prepared by the method.
The application of the lignin-unsaturated carboxylate composite reinforcing agent in rubber comprises the following steps:
(1) adding the lignin-unsaturated carboxylate composite reinforcing agent, rubber, carbon black, a vulcanizing agent and a vulcanizing aid into an internal mixer for mixing to obtain rubber compound;
(2) and (2) placing the mixed rubber obtained in the step (1) in an open mill for repeated thin passing, measuring the vulcanization performance by using a rubber vulcanization instrument, and performing hot press molding by using a flat plate vulcanizing machine.
In the step (1), the rubber is any one or more of natural rubber, styrene butadiene rubber and butadiene rubber; the carbon black is any one or the combination of two of high wear-resistant carbon black N330 and N660; the vulcanizing agent is sulfur or peroxide vulcanizing agent; wherein the vulcanization auxiliary agent is any one or combination of more of zinc oxide, stearic acid, N-cyclohexyl-2-benzothiazole sulfonamide, dibenzothiazole disulfide and tetramethyl thiuram disulfide; wherein, the peroxide vulcanizing agent is any one or more of dicumyl peroxide and di- (tert-butyl peroxy isopropyl) benzene.
In the step (1), the mass part ratio of the lignin-unsaturated carboxylate composite reinforcing agent to the rubber, the carbon black, the vulcanizing agent and the vulcanization accelerator is (2-40): 100: (1-25): (0.5-2.5): (0.5 to 10); the mixing temperature is 20-120 ℃, and the mixing time is 5-30 min; wherein, the banburying is preferably carried out for 20min at the temperature of 100 ℃.
The mass part ratio of the lignin-unsaturated carboxylate composite reinforcing agent to the rubber, the carbon black, the vulcanizing agent and the vulcanizing assistant is preferably 25: 100: 25: 2.5: 8.5.
the composite reinforcing agent is prepared by adding lignin and unsaturated carboxylate according to the mass part ratio of (1-25) to (1-15) directly into rubber, carbon black, a vulcanizing machine and a vulcanizing aid, wherein the mass part ratio of the lignin-unsaturated carboxylate composite reinforcing agent is 2-40.
In the step (2), the thin passing is to repeatedly extrude and shear the rubber compound through a roller of an open mill, and the number of thin passing is 5-30; the temperature of the plate vulcanizing machine is 120-180 ℃, and the hot pressing time is the positive vulcanization time t measured by a rubber vulcanizing instrument90。
Wherein the rubber vulcanization instrument is a M-3000A type vulcanization instrument of a high-speed rail detection instrument company Limited.
Has the advantages that: compared with the prior art, the invention has the following advantages:
1. according to the invention, lignin and unsaturated carboxylate are subjected to reactive grinding in grinding equipment, and the chelation between lignin polar groups and unsaturated carboxylate metal ions is utilized to greatly weaken intermolecular force of the lignin, so that the agglomeration of the lignin is weakened, and the dispersion of the lignin in a rubber matrix is facilitated.
2. The unsaturated carboxylate can promote the dispersion of lignin by chelating metal ions with the lignin, and generate ion crosslinking in the vulcanization process of rubber, thereby improving the mechanical property of the rubber.
3. The lignin-unsaturated carboxylate composite reinforcing agent can reach a finer particle size level (d) by using proper mechanical grinding equipment50Less than 20 μm, d90Less than 50 μm) to have a significant improvement effect on the mechanical properties of the rubber.
Drawings
FIG. 1 is a graph showing particle sizes of reinforcing agents in examples 1, 4, 5 and 1.
FIG. 2 is a view of optimizing the particle size of a reinforcing agent.
Detailed Description
The invention will be better understood from the following examples. However, those skilled in the art will readily appreciate that the description of the embodiments is only for illustrating the present invention and should not be taken as limiting the invention as detailed in the claims.
Example 1:
(1) uniformly mixing and stirring eucalyptus lignin and zinc methacrylate according to a mass ratio of 100:5, injecting the mixture and 0.8Mpa compressed air into an airflow crusher simultaneously, adding the crushed materials into a classification chamber for classification, wherein the rotating speed of a classifier is 8000rpm/min, returning the classified materials with the mesh number of less than 3000 to the airflow crusher for re-crushing, and discharging the classified materials with the mesh number of more than or equal to 3000 from a discharge port to obtain a lignin-zinc methacrylate composite reinforcing agent;
(2) weighing 10g of the composite reinforcing agent obtained in the step (1), sequentially adding 40g of natural rubber, 10g of high-wear-resistance carbon black N330, 1g of sulfur, 0.6g N-cyclohexyl-2-benzothiazole sulfonamide, 2g of zinc oxide and 0.8g of stearic acid into an internal mixer, and internally mixing for 20min at the temperature of 100 ℃;
(3) mixing the mixture obtained in the step (2)Placing the rubber compound in an open mill, thinly passing for 7 times, and obtaining the positive vulcanization time t at 180 ℃ by measuring the vulcanization performance with a rubber vulcanization instrument90And 3min, hot pressing for 3min by a flat vulcanizing machine at 180 ℃.
Example 2
(1) Uniformly mixing and stirring eucalyptus lignin and zinc methacrylate according to a mass ratio of 100:10, injecting the mixture and 0.8Mpa compressed air into an airflow crusher simultaneously, adding the crushed materials into a classification chamber for classification, wherein the rotating speed of a classifier is 8000rpm/min, returning the classified materials with the mesh number of less than 3000 to the airflow crusher for re-crushing, and discharging the classified materials with the mesh number of more than or equal to 3000 from a discharge port to obtain a lignin-zinc methacrylate composite reinforcing agent;
(2) weighing 10g of the composite reinforcing agent obtained in the step (1), sequentially adding 40g of natural rubber, 10g of high-wear-resistance carbon black N330, 1g of sulfur, 0.6g N-cyclohexyl-2-benzothiazole sulfonamide, 2g of zinc oxide and 0.8g of stearic acid into an internal mixer, and internally mixing for 20min at the temperature of 100 ℃;
(3) placing the mixed rubber obtained in the step (2) in an open mill for thin passing for 7 times, and measuring the vulcanization performance by a rubber vulcanization instrument to obtain the positive vulcanization time t at 180 DEG C90And 3min, hot pressing for 3min by a flat vulcanizing machine at 180 ℃.
Example 3
(1) Uniformly mixing and stirring eucalyptus lignin and zinc methacrylate according to a mass ratio of 100:20, injecting the mixture and 0.8Mpa compressed air into an airflow crusher simultaneously, adding the crushed materials into a classification chamber for classification, wherein the rotating speed of a classifier is 8000rpm/min, returning the classified materials with the mesh number of less than 3000 to the airflow crusher for re-crushing, and discharging the classified materials with the mesh number of more than or equal to 3000 from a discharge port to obtain a lignin-zinc methacrylate composite reinforcing agent;
(2) weighing 10g of the composite reinforcing agent obtained in the step (1), sequentially adding 40g of natural rubber, 10g of high-wear-resistance carbon black N330, 1g of sulfur, 0.6g N-cyclohexyl-2-benzothiazole sulfonamide, 2g of zinc oxide and 0.8g of stearic acid into an internal mixer, and internally mixing for 20min at the temperature of 100 ℃;
(3) placing the mixed rubber obtained in the step (2) in an open mill for thin passing for 7 times, and vulcanizing by using rubberThe positive vulcanization time t at 180 ℃ is obtained by measuring the vulcanization performance of the rubber90And hot pressing for 5min at 180 deg.C for 5 min.
Example 4
(1) Uniformly mixing and stirring eucalyptus lignin and zinc methacrylate according to a mass ratio of 100:5, adding the mixture into a hopper of an ultrafine pulverizer, adjusting the distance between grinding discs to be 5 mu m, rotating at 1500rpm/min, circulating for 3 times to fully grind the material to obtain a lignin-zinc methacrylate composite reinforcing agent, and measuring the particle size of the lignin-zinc methacrylate composite reinforcing agent;
(2) weighing 10g of the composite reinforcing agent obtained in the step (1), sequentially adding 40g of natural rubber, 10g of high-wear-resistance carbon black N330, 1g of sulfur, 0.6g N-cyclohexyl-2-benzothiazole sulfonamide, 2g of zinc oxide and 0.8g of stearic acid into an internal mixer, and internally mixing for 20min at the temperature of 100 ℃;
(3) placing the mixed rubber obtained in the step (2) in an open mill for thin passing for 7 times, and measuring the vulcanization performance by a rubber vulcanization instrument to obtain the positive vulcanization time t at 180 DEG C90And hot pressing for 6min at 180 deg.C for 6 min.
Example 5
(1) Adding the eucalyptus lignin and the zinc methacrylate into a ball milling tank according to the mass ratio of 100:5, adjusting the number of large balls and small balls to be 20:50, rotating the ball mill at 500rpm/min, alternately operating in the forward direction and the reverse direction for 4 times, each time for 30min, discharging after 2h, and measuring the particle size;
(2) weighing 10g of the composite reinforcing agent obtained in the step (1), sequentially adding 40g of natural rubber, 10g of high-wear-resistance carbon black N330, 1g of sulfur, 0.6g N-cyclohexyl-2-benzothiazole sulfonamide, 2g of zinc oxide and 0.8g of stearic acid into an internal mixer, and internally mixing for 20min at the temperature of 100 ℃;
(3) placing the mixed rubber obtained in the step (2) in an open mill for thin passing for 7 times, and measuring the vulcanization performance by a rubber vulcanization instrument to obtain the positive vulcanization time t at 180 DEG C90Hot pressing for 4min at 180 deg.C for 4min with a flat vulcanizing machine.
Example 6
(1) Adding corn straw lignin and magnesium methacrylate into a ball milling tank according to the mass ratio of 100:90, adjusting the number of large balls and small balls to be 20:50, rotating the ball mill at 600rpm/min, alternately operating forward and reverse directions for 4 times, each time for 35min, and discharging after 2 h;
(2) weighing 16g of the composite reinforcing agent obtained in the step (1), sequentially adding 40g of natural rubber, 10g of high-wear-resistance carbon black N330, 1g of sulfur, 0.6g N-cyclohexyl-2-benzothiazole sulfonamide, 2g of zinc oxide and 0.8g of stearic acid into an internal mixer, and mixing for 25min at the temperature of 120 ℃;
(3) placing the mixed rubber obtained in the step (2) in an open mill for thin passing for 10 times, and measuring the vulcanization performance by a rubber vulcanization instrument to obtain the positive vulcanization time t at 180 DEG C90And (3) performing hot pressing for 9min by a flat vulcanizing machine at 180 ℃ for 9min for molding.
Example 7
(1) Mixing and stirring the wheat straw lignin and the zinc acrylate uniformly according to the mass ratio of 200:50, injecting the mixture and 0.5Mpa compressed air into a jet mill simultaneously, adding the crushed materials into a classifier for classification, wherein the rotating speed of the classifier is 9000 rpm/min, returning the classified materials with the mesh number of less than 3000 to the jet mill for re-crushing, and discharging the classified materials with the mesh number of more than or equal to 3000 from a discharge hole to obtain the lignin-zinc acrylate composite reinforcing agent;
(2) weighing 2g of the composite reinforcing agent obtained in the step (1), sequentially adding 40g of natural rubber, 10g of high-wear-resistance carbon black N330, 1g of sulfur, 0.6g N-cyclohexyl-2-benzothiazole sulfonamide, 2g of zinc oxide and 0.8g of stearic acid into an internal mixer, and internally mixing for 20min at the temperature of 100 ℃;
(3) placing the mixed rubber obtained in the step (2) in an open mill for thin passing 11 times, and measuring the vulcanization performance by a rubber vulcanization instrument to obtain the positive vulcanization time t at 180 DEG C90Hot pressing for 10min at 180 deg.C for 10min with a flat vulcanizing machine.
Comparative example 1
(1) Mixing and stirring eucalyptus lignin and zinc methacrylate uniformly according to the mass ratio of 100:5 to obtain a lignin-zinc methacrylate composite reinforcing agent;
(2) weighing 10g of the composite reinforcing agent obtained in the step (1), sequentially adding 40g of natural rubber, 10g of high-wear-resistance carbon black N330, 1g of sulfur, 0.6g N-cyclohexyl-2-benzothiazole sulfonamide, 2g of zinc oxide and 0.8g of stearic acid into an internal mixer, and internally mixing for 20min at the temperature of 100 ℃;
(3) placing the mixed rubber obtained in the step (2) in an open mill for thin passing for 7 times, and measuring the vulcanization performance by a rubber vulcanization instrument to obtain the positive vulcanization time t at 180 DEG C90And hot pressing for 8min at 180 deg.C for 8 min.
Comparative example 2
(1) Injecting the eucalyptus lignin and 0.8Mpa compressed air into a jet mill simultaneously, adding the crushed materials into a classifier or a classifying chamber for classification, wherein the rotating speed of the classifier is 8000rpm/min, returning the classified materials with the mesh number less than 3000 to the jet mill for re-crushing, and discharging the classified materials with the mesh number more than or equal to 3000 from a discharge hole;
(2) weighing 10g of the material obtained in the step (1), sequentially adding 40g of natural rubber, 10g of high-wear-resistance carbon black N330, 1g of sulfur, 0.6g N-cyclohexyl-2-benzothiazole sulfonamide, 2g of zinc oxide and 0.8g of stearic acid into an internal mixer, and internally mixing for 20min at the temperature of 100 ℃;
(3) placing the mixed rubber obtained in the step (2) in an open mill for thin passing for 7 times, and measuring the vulcanization performance by a rubber vulcanization instrument to obtain the positive vulcanization time t at 180 DEG C90Is 6.5min, and is molded by hot pressing with a flat vulcanizing machine at 180 deg.C for 6.5 min.
Comparative example 3:
(1) injecting zinc methacrylate and 0.8Mpa compressed air into a jet mill simultaneously, adding the crushed materials into a grading chamber for grading, wherein the rotating speed of a classifier is 8000rpm/min, returning the materials with the graded mesh number of less than 3000 to the jet mill for re-crushing, and discharging the materials with the graded mesh number of more than or equal to 3000 from a discharge hole to obtain the lignin-zinc methacrylate composite reinforcing agent;
(2) weighing 10g of the material obtained in the step (1), sequentially adding 40g of natural rubber, 10g of high-wear-resistance carbon black N330, 1g of sulfur, 0.6g N-cyclohexyl-2-benzothiazole sulfonamide, 2g of zinc oxide and 0.8g of stearic acid into an internal mixer, and internally mixing for 20min at the temperature of 100 ℃;
(3) placing the mixed rubber obtained in the step (2) in an open mill for thin passing for 7 times, and measuring the vulcanization performance by a rubber vulcanization instrument to obtain the positive vulcanization time t at 180 DEG C90Hot pressing for 7min at 180 deg.C for 7minAnd (5) molding.
Comparative example 4:
(1) weighing 10g of eucalyptus lignin, sequentially adding 40g of natural rubber, 10g of high-wear-resistance carbon black N330, 1g of sulfur, 0.6g N-cyclohexyl-2-benzothiazole sulfonamide, 2g of zinc oxide and 0.8g of stearic acid into an internal mixer, and internally mixing for 20min at 100 ℃;
(2) placing the mixed rubber obtained in the step (2) in an open mill for thin passing for 7 times, and measuring the vulcanization performance by a rubber vulcanization instrument to obtain the positive vulcanization time t at 180 DEG C90And hot pressing for 6min at 180 deg.C for 6 min. Comparative example 5:
(1) weighing 10g of zinc methacrylate, and adding 40g of natural rubber, 10g of high-wear-resistance carbon black N330, 1g of sulfur, 0.6g N-cyclohexyl-2-benzothiazole sulfonamide, 2g of zinc oxide and 0.8g of stearic acid into an internal mixer in sequence, and internally mixing for 20min at the temperature of 100 ℃;
(2) placing the mixed rubber obtained in the step (2) in an open mill for thin passing for 7 times, and measuring the vulcanization performance by a rubber vulcanization instrument to obtain the positive vulcanization time t at 180 DEG C90And hot pressing for 6min at 180 deg.C for 6 min.
The rubbers of examples 1-5 and comparative examples 1 and 2 were tested, wherein the particle size distribution was determined by a U.S. macchian S3500 laser particle size analyzer; the tensile property is tested on a UTM6104 electronic universal tester according to GB/T528-2009; hardness testing method the strips were placed on a shore durometer a and the handle was pressed down so that the durometer was pressed down into horizontal contact with the sample and the reading was taken within 1 s.
As can be seen from the particle size distribution (table 1) and mechanical properties (table 2) of examples 1, 2 and 3, the particle size of the reinforcing agent can be further reduced by mechanical grinding with an increase in the amount of zinc methacrylate added under the same grinding conditions, thereby improving the reinforcing effect.
As can be seen from the particle size diagrams and particle size optimization (fig. 1 and fig. 2) of examples 1, 4 and 5 and comparative example 1, the smaller the particle size is, the better the mechanical strength of the rubber is, and from the viewpoint of grinding effect, the jet milling > ultrafine grinding > ball milling > unground, the particle size of the reinforcing agent prepared by jet milling is the smallest, and the reinforcing effect on the rubber is the best.
As can be seen from the particle size distribution (Table 1) and the mechanical properties (Table 2) of the example 1 and the comparative example 2, the addition of zinc methacrylate can improve the grinding effect, so that the particle size of the ground material is smaller, and the mechanical properties of the vulcanized rubber are better; as can be seen from the particle size distribution (Table 1) and the mechanical properties (Table 2) of example 3 and comparative example 3, when lignin is compounded with a small amount of zinc methacrylate, the mechanical properties of the reinforced rubber are close to the mechanical properties of the rubber completely reinforced with zinc methacrylate, which shows that the small amount of zinc methacrylate can significantly improve the dispersibility of lignin in a rubber matrix, and further proves that the unsaturated carboxylate can actually promote the dispersion of lignin by chelating metal ions with lignin, and generate ionic crosslinking during the vulcanization of the rubber, thereby improving the mechanical properties of the rubber.
TABLE 1 particle size distribution of reinforcing agent for examples and comparative examples
TABLE 2 mechanical Properties of vulcanizates of examples and comparative examples
The invention provides a thought and a method for a lignin-unsaturated carboxylate composite reinforcing agent and application thereof in rubber, and a method and a way for realizing the technical scheme are many, the above description is only a preferred embodiment of the invention, and it should be noted that for a person skilled in the art, a plurality of improvements and decorations can be made without departing from the principle of the invention, and the improvements and decorations are also regarded as the protection scope of the invention. All the components not specified in the present embodiment can be realized by the prior art.
Claims (7)
1. The application of the lignin-unsaturated carboxylate composite reinforcing agent in the preparation of rubber is characterized in that the preparation method of the lignin-unsaturated carboxylate comprises the following steps: adding lignin and unsaturated carboxylate into grinding equipment, and adjusting the process until the particle size of the material is d50Less than 20 μm, d90Below 50 μm;
wherein, the unsaturated carboxylate is zinc methacrylate;
wherein the mass part ratio of the lignin to the unsaturated carboxylate is (1-25): (1-15).
2. The use of claim 1, wherein the lignin is any one or more of herbaceous lignin, hardwood lignin, softwood lignin, and lignin modified by the aforementioned lignin.
3. The use according to claim 1, wherein the milling apparatus is any one of a ball mill, an ultra-fine pulverizer, and a jet mill.
4. The use according to claim 1, wherein the rubber is prepared by a process comprising the steps of:
(1) adding the lignin-unsaturated carboxylate composite reinforcing agent, rubber, carbon black, a vulcanizing agent and a vulcanizing aid into an internal mixer for mixing to obtain rubber compound;
(2) and (2) placing the mixed rubber obtained in the step (1) in an open mill for repeated thin passing, measuring the vulcanization performance by using a rubber vulcanization instrument, and performing hot press molding by using a flat plate vulcanizing machine.
5. The use according to claim 4, wherein in the step (1), the rubber is any one or more of natural rubber, styrene-butadiene rubber and butadiene rubber; the carbon black is any one or the combination of two of high wear-resistant carbon black N330 and N660; the vulcanizing agent is sulfur or peroxide vulcanizing agent; the vulcanizing assistant is any one or combination of zinc oxide, stearic acid, N-cyclohexyl-2-benzothiazole sulfonamide, dibenzothiazole disulfide and tetramethyl thiuram disulfide.
6. The application of the composite material as claimed in claim 4, wherein in the step (1), the mass part ratio of the lignin-unsaturated carboxylate composite reinforcing agent to the rubber, the carbon black, the vulcanizing agent and the vulcanizing assistant is (2-40): 100: (1-25): (0.5-2.5): (0.5 to 10); the mixing temperature is 20-120 ℃, and the mixing time is 5-30 min.
7. The use according to claim 4, wherein in the step (2), the number of thin passes is 5-30; the temperature of the plate vulcanizing machine is 120-180 ℃, and the hot pressing time is the positive vulcanization time t measured by a rubber vulcanizing instrument90。
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| CN113583254B (en) * | 2021-07-28 | 2022-08-02 | 南京工业大学 | Cross-linkable lignin, preparation method thereof and application thereof in rubber composite material |
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