CN115477851B - Environment-friendly modified rubber homogenizing agent, preparation method thereof and product - Google Patents
Environment-friendly modified rubber homogenizing agent, preparation method thereof and product Download PDFInfo
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- CN115477851B CN115477851B CN202111409479.0A CN202111409479A CN115477851B CN 115477851 B CN115477851 B CN 115477851B CN 202111409479 A CN202111409479 A CN 202111409479A CN 115477851 B CN115477851 B CN 115477851B
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 86
- 239000005060 rubber Substances 0.000 title claims abstract description 86
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000003208 petroleum Substances 0.000 claims abstract description 73
- 239000000463 material Substances 0.000 claims abstract description 56
- 239000010426 asphalt Substances 0.000 claims abstract description 49
- 229920005989 resin Polymers 0.000 claims abstract description 33
- 239000011347 resin Substances 0.000 claims abstract description 33
- 239000003607 modifier Substances 0.000 claims abstract description 25
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- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 150000008064 anhydrides Chemical group 0.000 claims abstract description 5
- 239000004636 vulcanized rubber Substances 0.000 claims description 21
- 244000043261 Hevea brasiliensis Species 0.000 claims description 18
- 229920003052 natural elastomer Polymers 0.000 claims description 18
- 229920001194 natural rubber Polymers 0.000 claims description 18
- 239000003292 glue Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229920005555 halobutyl Polymers 0.000 claims description 4
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 abstract description 10
- 229920005556 chlorobutyl Polymers 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000002156 mixing Methods 0.000 description 8
- 239000000945 filler Substances 0.000 description 7
- 238000004513 sizing Methods 0.000 description 7
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- 238000004073 vulcanization Methods 0.000 description 5
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- 238000012545 processing Methods 0.000 description 3
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
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- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
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- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
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- 238000004220 aggregation Methods 0.000 description 1
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- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
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- 229910021389 graphene Inorganic materials 0.000 description 1
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- 238000007373 indentation Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
- C08L23/283—Halogenated homo- or copolymers of iso-olefins
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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)
- Engineering & Computer Science (AREA)
- Civil Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the IPC field of C08L95/00, in particular to an environment-friendly modified rubber homogenizing agent, a preparation method and a product thereof. The preparation raw materials of the environment-friendly modified rubber homogenizing agent comprise petroleum asphalt, petroleum resin and a modifying agent; the softening point of the petroleum asphalt is not lower than 70 ℃; the petroleum resin is a plurality of mixed resins in C4-C9, and the modifier is anhydride. In the application, when the modifier is added into the petroleum asphalt with a high softening point and the homogenizing agent is prepared at a high temperature, the polycyclic aromatic hydrocarbon in the petroleum asphalt reacts with the maleic anhydride and the citraconic anhydride containing unsaturated double bonds at a high temperature, so that the polycyclic aromatic hydrocarbon content of the product is obviously reduced, three types of standards required at present are met, and even a higher level is achieved. In addition, when the homogenizing agent is added into the traditional rubber material, the compatibility of raw materials in the material can be obviously improved, and the properties of the prepared material such as tearing strength, mechanical strength and the like are improved, so that the rubber material with excellent comprehensive properties is obtained.
Description
Technical Field
The invention relates to the IPC field of C08L95/00, in particular to an environment-friendly modified rubber homogenizing agent, a preparation method and a product thereof.
Background
The homogenizing agent is a processing aid which contains different polar structures and can be compatible with rubber with various polarities, so that the problem that the rubber with different polarities is difficult to disperse uniformly can be solved. Because the conventional homogenizing agent contains a part of low molecular weight structure, the homogenizing agent has certain plasticizing and lubricating effects in the processing process, can obviously improve the processing performance of the rubber compound, promote the dispersion of the filler and save energy consumption. Therefore, the homogenizing agent is an important processing aid in the rubber industry. Along with the improvement of environmental awareness, the environmental protection requirements of people on various industrial products are increasingly strict, the rubber industry is particularly remarkable, and the development of the high-quality environmental-protection homogenizing agent has extremely important significance for the rubber industry as an important processing aid in the rubber industry.
For example, chinese patent CN 201210286698 discloses an environment-friendly rubber plasticizing homogenizing agent, wherein components such as heavy petroleum asphalt, tar and petroleum resin with softening points of 40-70 ℃ are adopted to prepare the rubber plasticizing homogenizing agent, and the problems of bubbling, kettle overflow and the like generated in the preparation process of the traditional homogenizing agent are solved. However, since the petroleum asphalt used therein is low softening point asphalt, its temperature sensitivity is strong, and its dimensional stability is affected to some extent when the petroleum asphalt is applied to rubber products. Moreover, the effect of the homogenizing agent is exerted by the interaction between the polar groups and the nonpolar groups in the structure of the homogenizing agent and other components in the system, and the softening agent of the homogenizing agent is low and has weak cohesive strength, so that the homogenizing agent is easy to migrate, the tearing strength of a product is reduced, the service life is shortened, and particularly, the influence on the performance of the system is particularly obvious aiming at the system with high filler content and relatively close difference between polar glue and nonpolar glue content.
Disclosure of Invention
In view of the above technical problems, a first aspect of the present invention provides an environmentally-friendly modified rubber homogenizing agent, which is prepared from petroleum asphalt, petroleum resin and a modifier; the softening point of the petroleum asphalt is not lower than 70 ℃; the petroleum resin is a plurality of mixed resins in C4-C9, and the modifier is anhydride.
The environment-friendly modified rubber homogenizing agent is prepared from petroleum asphalt, petroleum resin and a modifying agent, wherein the petroleum asphalt is a product in the crude oil processing process. The petroleum asphalt is high-softening-point petroleum asphalt, and the softening point of the petroleum asphalt is 70-120 ℃ as a preferable technical scheme of the invention. As an example, the petroleum asphalt may have a softening point of 70 ℃, 71 ℃, 72 ℃, 73 ℃, 74 ℃, 75 ℃, 76 ℃, 77 ℃, 78 ℃, 79 ℃, 80 ℃, 81 ℃, 82 ℃, 83 ℃, 84 ℃, 85 ℃, 86 ℃, 87 ℃, 88 ℃, 89 ℃, 90 ℃, 91 ℃, 92 ℃, 93 ℃, 94 ℃, 95 ℃, 96 ℃, 97 ℃, 98 ℃, 99 ℃, 100 ℃, 101 ℃, 102 ℃, 103 ℃, 104 ℃, 105 ℃, 106 ℃, 107 ℃, 108 ℃, 109 ℃, 110 ℃, 111 ℃, 112 ℃, 113 ℃, 114 ℃, 115 ℃, 116 ℃, 117 ℃, 118 ℃, 119 ℃, 120 ℃, etc. The petroleum asphalt of the invention is used in an amount of 55-99.5wt%. The softening point described in the present invention is a temperature dependence characteristic of its heat softening and can be measured in a manner conventional in the art, such as by the ring and ball method. The specific choice of petroleum asphalt to meet the above requirements is not particularly limited in the present invention, and may be selected from related products commercially available from the market, which are well known to those skilled in the art.
The petroleum resin is a mixture of a plurality of C4-C9 resins, the polar structure of the product can be improved through different petroleum resins, and the petroleum resin is better suitable for glue species with different polarities. Preferably, the petroleum resin of the present invention is used in an amount of 0 to 40wt%.
The modifier in the present invention is an acid anhydride, which may be an acid anhydride of an aliphatic dibasic acid such as maleic anhydride, citraconic anhydride, succinic anhydride, etc.; anhydrides of aromatic dibasic acids such as phthalic anhydride and the like are also possible. Further preferably, the modifier is maleic anhydride (CAS: 108-31-6) and/or citraconic anhydride (CAS: 616-02-4). Further preferably, the mass ratio of the maleic anhydride to the citraconic anhydride is (1-3): 1, a step of; further, the mass ratio of the maleic anhydride to the citraconic anhydride is 1.8:1. the applicant finds that by adopting maleic anhydride and citraconic anhydride in specific proportions as modifiers, the dispersion performance of the prepared uniformity agent on sizing materials can be improved, even for small differences in the component proportions of polar and nonpolar collagen materials, a uniform continuous phase and disperse phase sizing material system cannot be formed, and the dispersion effect of the uniformity agent is still very strong.
As a preferred embodiment of the present invention, the modifier may be used in an amount of 0.5 to 5wt% based on the amount of the petroleum asphalt, and may be exemplified by 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1.0wt%, 1.1wt%, 1.2wt%, 1.5wt%, 1.8wt%, 2.0wt%, 2.3wt%, 2.5wt%, 2.8wt%, 3.0wt%, 3.2wt%, 3.5wt%, 3.8wt%, 4.0wt%, 4.2wt%, 4.5wt%, 4.8wt%, 5.0wt%, etc.
In the application, when the modifier is added into the petroleum asphalt with a high softening point and the homogenizing agent is prepared at a high temperature, the polycyclic aromatic hydrocarbon in the petroleum asphalt reacts with the maleic anhydride and the citraconic anhydride containing unsaturated double bonds at a high temperature, so that the polycyclic aromatic hydrocarbon content of the product is obviously reduced, three types of standards required at present are met, and even a higher level is achieved.
The second aspect of the invention provides a preparation method of the environment-friendly modified rubber homogenizing agent, which is characterized by comprising the following steps: heating petroleum asphalt and petroleum resin to 100-220 ℃ according to the proportion to melt, then adding modifier in batches to stir and mix, and reacting for 0.5-3 h under heat preservation to obtain the environment-friendly modified rubber.
In order to control the reaction degree and make the reaction more stable, the modifier is not added at one time, but gradually added dropwise (namely, added dropwise in batches). The reaction temperature between the petroleum asphalt and the modifier in the invention can be adjusted according to the reaction intensity in the reaction process, the reaction temperature is preferably 140-210 ℃, and the reaction temperature can be 140 ℃, 150 ℃, 160 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, 201 ℃, 202 ℃, 203 ℃, 204 ℃, 205 ℃, 206 ℃, 207 ℃, 208 ℃, 209 ℃, 210 ℃ and the like; preferably, the reaction temperature is 210 ℃.
The third aspect of the present invention provides a heat vulcanized rubber material, comprising the environmentally-friendly modified rubber homogenizing agent as described above, wherein the content of the environmentally-friendly modified rubber homogenizing agent in the heat vulcanized rubber material is 2.8-8.5 wt%; illustratively, the content of the environmentally friendly modified rubber homogenizing agent may be 2.8wt%, 3.0wt%, 3.2wt%, 3.5wt%, 7wt%, 3.8wt%, 4.0wt%, 4.1wt%, 4.2wt%, 4.5wt%, 4.7wt%, 4.9wt%, 5.0wt%, 5.2wt%, 5.3wt%, 5.5wt%, 5.7wt%, 5.9wt%, 6.0wt%, 6.2wt%, 6.5wt%, 6.8wt%, 7.0wt%, 7.5wt%, 7.8wt%, 8.0wt%, 8.2wt%, 8.5wt%, etc.
As a preferable technical scheme of the invention, the hot vulcanized rubber material comprises the following components in parts by weight:
preferably, the dosage of the environment-friendly modified rubber homogenizing agent is 5-12 parts.
The specific choice of the rubber base material is not particularly limited in the present invention, and various rubber base material components which are conventionally required to be added with a homogenizing agent in the field can be selected, and generally comprise both a polar rubber material and a nonpolar rubber material, including but not limited to styrene-butadiene rubber, natural rubber, chloroprene rubber, chlorinated butyl rubber, chlorinated rubber, ethylene propylene diene monomer rubber, butadiene rubber, etc.
As a preferable technical scheme of the invention, the rubber base material is wrapped with polar glue and nonpolar glue; the content of the nonpolar glue in the rubber base stock is not less than 15wt%; the non-polar gum includes natural rubber.
The rubber base material is a sizing material with relatively small content difference between polar rubber and nonpolar rubber. When the polar rubber is mainly used in the rubber base material contained in the rubber material system, a small amount of nonpolar rubber is added for auxiliary mixing; or, when the nonpolar glue is used as the main material and a small amount of polar glue is added to assist in mixing, the mixing effect is poor due to the difference between the polarities of the nonpolar glue, but the sufficient dispersion can be realized only by a small amount of the homogenizing agent, so that the problem of poor compatibility is solved. However, when the contents of the polar rubber and the nonpolar rubber are close to each other or the content of the auxiliary rubber in the system is higher, the cohesive energy density difference of the two rubber materials is larger, and the materials cannot be fully fused and diffused between polymer chain segments during fusion and diffusion, so that obvious interfaces exist between the material particles, and the compatibility is obviously deteriorated. Even if the homogenizing agent is added, the compatibility problem can be slightly improved by utilizing the functions of polar and nonpolar groups in the structure of the homogenizing agent, but the content difference of two sizing materials is not large enough, so that stable continuous phases and disperse phases cannot be formed, and materials form different aggregation states on microcosmic scale, and the compatibility is influenced. In the application, the uniformity agent prepared from the specific raw materials can shorten the cohesive energy density difference between polar rubber such as halogenated butyl rubber and nonpolar rubber such as natural rubber, so that good compatibility can be realized under the action of a small amount of uniformity agent.
As a preferable technical scheme of the invention, the content of the nonpolar glue in the rubber base stock is not less than 20wt%. Further, the rubber base consists of 75wt% of halogenated butyl rubber (preferably chlorinated butyl rubber) and 25wt% of natural rubber.
The filler in the present invention is an inorganic filler component, and the specific choice thereof is not particularly limited in the present invention, and filler components conventional in the art may be selected, including, but not limited to, white carbon black, black carbon black, calcium carbonate, kaolin, graphene, etc., such as carbon black N600, etc.
The tackifying resin is a component for adjusting the viscosity of a sizing system, and as a preferable technical scheme, the tackifying resin is one or more of C5 petroleum resin, C9 petroleum resin, rosin resin and the like.
The process oil is a high boiling fraction of petroleum, the specific choice of which is not particularly required, and various process oils known to those skilled in the art can be selected, including but not limited to conventional environmentally friendly aromatic oils and the like in the art.
The vulcanization accelerator is an auxiliary sulfur component for crosslinking and vulcanizing the rubber base material, and the specific choice of the vulcanization accelerator is not particularly limited, and various accelerators known to those skilled in the art can be selected, including but not limited to DM and the like.
The preparation method of the heat vulcanized rubber material is not particularly limited, and the heat vulcanized rubber material can be prepared according to a conventional method in the field, for example, the heat vulcanized rubber material can be obtained by blending all raw materials and vulcanizing at 160 ℃ for 20 min.
The technical scheme provided by the invention has the following beneficial effects that：
When the modifier is added into the homogenizing agent provided by the invention and the homogenizing agent is prepared at high temperature, the polycyclic aromatic hydrocarbon in the petroleum asphalt reacts with the maleic anhydride and the citraconic anhydride containing unsaturated double bonds at high temperature, so that the polycyclic aromatic hydrocarbon content of the product is obviously reduced, three types of standards required at present are met, and even the level is higher. In addition, when the homogenizing agent is added into the traditional rubber material, the compatibility of raw materials in the material can be obviously improved, the tearing strength, mechanical strength and other performances of the prepared material are improved, and the cohesive energy density difference between polar rubber such as halogenated butyl rubber and nonpolar rubber such as natural rubber can be shortened by adopting the homogenizing agent prepared from the specific raw materials, so that the good compatibility can be realized under the action of a small amount of the homogenizing agent, and the rubber material with excellent comprehensive performance is obtained.
Detailed Description
Examples1
The embodiment provides an environment-friendly modified rubber homogenizing agent, which is prepared from 79.5 parts by weight of petroleum asphalt, 20 parts by weight of petroleum resin and 0.5 part by weight of maleic anhydride modifier; the softening point of the petroleum asphalt is 90 ℃. The preparation method of the environment-friendly modified rubber comprises the following steps: and (3) weighing 100 parts by weight of petroleum asphalt, heating to 210 ℃ to melt, then gradually adding 0.5 part by weight of maleic anhydride modifier, stirring and mixing, and carrying out heat preservation reaction for 1h to obtain the environment-friendly modified rubber.
Examples2
The embodiment provides an environment-friendly modified rubber homogenizing agent, which is prepared from 79 parts by weight of petroleum asphalt, 20 parts by weight of petroleum resin and 1.0 part by weight of maleic anhydride modifier; the softening point of the petroleum asphalt was 90 ℃ (the same petroleum asphalt as in example 1). The preparation method of the environment-friendly modified rubber comprises the following steps: and (3) weighing 100 parts by weight of petroleum asphalt, heating to 210 ℃ to melt, then gradually adding 1.0 part by weight of maleic anhydride modifier, stirring and mixing, and carrying out heat preservation reaction for 1h to obtain the environment-friendly modified rubber.
Examples3
The embodiment provides an environment-friendly modified rubber homogenizing agent, which is prepared from 79.5 parts by weight of petroleum asphalt, 20 parts by weight of petroleum resin and 0.5 part by weight of citraconic anhydride modifier; the softening point of the petroleum asphalt was 90 ℃ (the same petroleum asphalt as in example 1). The preparation method of the environment-friendly modified rubber comprises the following steps: and (3) weighing 100 parts by weight of petroleum asphalt, heating to 210 ℃ to melt, then gradually adding 0.5 part by weight of citraconic anhydride modifier, stirring and mixing, and carrying out heat preservation reaction for 1h to obtain the environment-friendly modified rubber.
Examples4
The embodiment provides an environment-friendly modified rubber homogenizing agent, which is prepared from 79 parts by weight of petroleum asphalt, 20 parts by weight of petroleum resin and 1.0 part by weight of citraconic anhydride modifier; the softening point of the petroleum asphalt was 90 ℃ (the same petroleum asphalt as in example 1). The preparation method of the environment-friendly modified rubber comprises the following steps: and (3) weighing 100 parts by weight of petroleum asphalt, heating to 210 ℃ to melt, then gradually adding 1.0 part by weight of citraconic anhydride modifier, stirring and mixing, and carrying out heat preservation reaction for 1h to obtain the environment-friendly modified rubber.
Performance testing
The applicant carried out 18 polycyclic aromatic hydrocarbon content tests on the samples of the above examples according to ASTM D5186, using petroleum asphalt as a control, the test results of which are shown in table 1 below:
TABLE 1
| Sample of | 18 polycyclic aromatic hydrocarbons total per ppm |
| Petroleum asphalt | 108.7 |
| Example 1 | 5.2 |
| Example 2 | 6.2 |
| Example 3 | 10.1 |
| Example 4 | 8.0 |
Wherein 18 polycyclic aromatic hydrocarbons total < 50ppm are the minimum requirement of three classes. From the experimental results, the polycyclic aromatic hydrocarbon content of the product can be obviously reduced after the modification by the method disclosed by the invention, the three types of standards required at present are met, and even the level is higher.
Examples5
The embodiment provides a heat vulcanized rubber material, which comprises the following components in parts by weight:
wherein the rubber base consists of 75wt% of chlorinated butyl rubber and 25wt% of natural rubber, and the rubber type adopted by the chlorinated butyl rubber is CIIR 1240); the natural rubber is Vietnam natural rubber of ZheMinyuan International trade company; the tackifying resin is C5 petroleum resin; the filler is N600 carbon black.
Examples6
The embodiment provides a heat vulcanized rubber material, which comprises the following components in parts by weight:
wherein the rubber base consists of 75wt% of chlorinated butyl rubber and 25wt% of natural rubber, and the rubber type adopted by the chlorinated butyl rubber is CIIR 1240); the natural rubber is Vietnam natural rubber of ZheMinyuan International trade company; the tackifying resin is C5 petroleum resin; the filler is N600 carbon black.
Examples7
The embodiment provides a heat vulcanized rubber material, which comprises the following components in parts by weight:
wherein the rubber base consists of 75wt% of chlorinated butyl rubber and 25wt% of natural rubber, and the rubber type adopted by the chlorinated butyl rubber is CIIR 1240); the natural rubber is Vietnam natural rubber of ZheMinyuan International trade company; the tackifying resin is C5 petroleum resin; the filler is N600 carbon black. Wherein the 40MSF homogenizing agent is an industry standard product.
Performance testing
The applicant blended the sample materials of examples 5 to 7 above and then vulcanized for 20 minutes at 160℃to obtain test samples, which were recorded as SP-1, SP-2 and SP-3, respectively, and then tested the mechanical properties according to GB/T528-2009 "determination of tensile stress strain properties of vulcanized rubber or thermoplastic rubber", GB/T529-2009 "determination of tear Strength (Right angle shape) of vulcanized rubber or thermoplastic rubber", and GB/T531.1-2008 "method of indentation hardness experiment of vulcanized rubber or thermoplastic rubber". The test results are shown in the following table 2:
TABLE 2
| SP-1 | SP-2 | SP-3 | |
| hardness/Shore A | 50 | 50 | 50 |
| 100% stress/(MPa) of stretching | 1.2 | 1.2 | 1.3 |
| 300% stress/(MPa) of stretching | 4.1 | 3.9 | 4.2 |
| Elongation at break/(%) | 632 | 670 | 622 |
| Tensile strength/(MPa) | 8.9 | 9.0 | 8.9 |
| Tear strength/(kN/m) | 39.21 | 39.54 | 39.21 |
From the experimental results, the uniformity agent is added into the rubber system, so that the compatibility among materials can be improved well, and the comprehensive performance of the rubber material can be improved. The overall performance of the samples obtained with the addition of the homogenizers of the present application was comparable to the samples obtained with the addition of the same amount of the commercial homogenizers for the standard product 40 MSF.
Examples8
This example provides a heat vulcanized rubber material whose raw material for production differs from that of example 6 in that the rubber base material consists of 70% by weight of chlorinated butyl rubber and 30% by weight of natural rubber. In addition, the modifier in the used homogenizing agent is a mixture of maleic anhydride and citraconic anhydride in a mass ratio of 1.8:1, and the homogenizing agent is prepared in the same manner as in example 6. The remaining raw materials of the heat-vulcanized rubber material in this case, the vulcanization method of the material, and the like are the same as those of example 6. The tensile strength obtained by testing the sample obtained by the method is 9.1MPa, the tearing strength is 40.10kN/m, the elongation at break is 639%, and compared with an SP-2 sample, the comprehensive performance of the sample is not obviously reduced due to the change of the proportion of the polar glue and the nonpolar glue in the system.
Further, the applicant found that when a heavy-duty petroleum asphalt having a softening point of about 55℃was used in the leveling agent, and 0.5 parts of maleic anhydride was added per 100 parts by mass of such petroleum asphalt to modify it to obtain the leveling agent, and after adding it to the hot vulcanized rubber material in example 5 (replacing the leveling agent therein), it was found that the tear strength was lowered as compared with SP-1 after vulcanization and performance test were carried out in the same manner, resulting in 37.86kN/m. While the homogenizing agent was added to the sample in example 5, and the proportion of the components in the rubber base material was adjusted to 70% by weight of chlorinated butyl rubber and 30% by weight of natural rubber, the 100% elongation stress of the sample obtained by vulcanization under the same conditions was 1.5MPa and the elongation at break was only 570%. It can be seen that the softening point of the petroleum asphalt used in the homogenizing agent has an important influence on the dispersibility of the obtained homogenizing agent on the raw materials of the rubber material, and if the softening point is improperly regulated, the compatibility among the raw materials of the heat vulcanized rubber material can be influenced, especially for the case that the proportion difference of the dosage form sizing material and the nonpolar sizing material is smaller, the influence on the softening point of the petroleum asphalt in the homogenizing agent is more obvious.
Claims (7)
1. An environment-friendly modified rubber homogenizing agent is characterized in that the preparation raw materials comprise petroleum asphalt, petroleum resin and a modifying agent; the softening point of the petroleum asphalt is 70-120 ℃; the petroleum resin is a plurality of mixed resins in C4-C9; the modifier is anhydride; the petroleum asphalt is used in an amount of 55-99.5wt%; the petroleum resin is used in an amount of 0-40wt%; the dosage of the modifier is 0.5-5 wt%;
the anhydride is maleic anhydride and/or citraconic anhydride.
2. The method for preparing the environment-friendly modified rubber homogenizing agent according to claim 1, which is characterized by comprising the following steps: heating petroleum asphalt and petroleum resin to 100-220 ℃ according to the proportion to melt, then adding modifier in batches to stir and mix, and reacting for 0.5-3 h under heat preservation to obtain the environment-friendly modified rubber.
3. A heat vulcanized rubber material, characterized in that it comprises the environmentally friendly modified rubber homogenizing agent according to claim 1, wherein the content of the environmentally friendly modified rubber homogenizing agent in the heat vulcanized rubber material is 2.8-8.5 wt%.
4. A heat vulcanizable rubber material according to claim 3, characterized in that it comprises the following components in parts by weight:
5. the heat vulcanized rubber material according to claim 4, wherein said rubber base material is coated with a polar gum and a nonpolar gum; the content of the nonpolar glue in the rubber base stock is not less than 15wt%; the non-polar gum includes natural rubber.
6. The heat vulcanized rubber material as defined in claim 4, wherein the content of said nonpolar rubber in said rubber base is not less than 20wt%.
7. The heat vulcanized rubber material as defined in claim 4, wherein said rubber base is composed of 75 wt.% halogenated butyl rubber and 25 wt.% natural rubber.
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