CN108410039B - Modified powder nitrile rubber and preparation method thereof - Google Patents
Modified powder nitrile rubber and preparation method thereof Download PDFInfo
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- CN108410039B CN108410039B CN201810350866.3A CN201810350866A CN108410039B CN 108410039 B CN108410039 B CN 108410039B CN 201810350866 A CN201810350866 A CN 201810350866A CN 108410039 B CN108410039 B CN 108410039B
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- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
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Abstract
The invention discloses modified powder nitrile rubber and a preparation method thereof. The modified powder nitrile rubber comprises the following components in parts by weight: 100 parts of nitrile rubber, 10-30 parts of calcium polymethacrylate and 10-30 parts of calcium terephthalate. The preparation method of the modified powder nitrile rubber comprises the following steps: (1) preparing a homogeneous aqueous dispersion of methacrylic acid, terephthalic acid, nitrile latex and a vulcanizing agent; (2) then reacting with calcium hydroxide under the action of an emulsifying machine, filtering and drying; (3) mixing in an internal mixer to obtain mixed rubber; (4) and vulcanizing the rubber compound, and then treating by a grinding process to obtain the modified powdery nitrile rubber. The modified powdery nitrile rubber is uniformly dispersed in the polyvinyl chloride main body material, so that the toughness of the product can be improved, and the rigidity and the heat resistance are well maintained.
Description
Technical Field
The invention belongs to the field of high polymer materials, and relates to modified powdered nitrile rubber and a preparation method thereof.
Background
The hard polyvinyl chloride (PVC-U) is mainly applied to three fields of building materials, electronic appliances and packaging. It has the advantages of light weight, low manufacturing cost, convenient construction and maintenance, etc. However, the hard PVC plastic is a brittle material, and the further development and application of the hard PVC plastic are greatly limited by the defects of poor toughness, low heat resistance, poor thermal stability and the like. A series of mature routes and methods such as copolymerization, blending and the like are formed for toughening and modifying PVC-U, wherein the blending toughening modification method is most applied, and the powdered nitrile rubber is a modified material with a remarkable toughening effect.
However, although the powder nitrile rubber can improve the impact resistance, the elongation at break and the low-temperature performance of the hard PVC, the rigidity and the heat resistance of the material are reduced to different degrees along with the improvement of the impact toughness of the blend, and new defects are brought to the product. Therefore, it is urgent to develop a multifunctional toughening material which can improve the toughness of the material and also can improve the rigidity and heat resistance of the material.
Disclosure of Invention
The invention aims to solve the technical problem of providing modified powdered nitrile rubber and a preparation method thereof, wherein the modified powdered nitrile rubber prepared by the method can be uniformly dispersed in a PVC-U main body material, and the prepared PVC-U product has good toughness and good rigidity and heat resistance.
In order to achieve the purpose, the invention is realized by the following technical scheme: the invention relates to modified powdered nitrile rubber, which comprises the following components in parts by weight:
100 parts of nitrile-butadiene rubber,
10-30 parts of calcium polymethacrylate,
10-30 parts of calcium terephthalate.
The preparation method of the modified powder nitrile rubber comprises the following process steps:
(1) dispersing methacrylic acid and terephthalic acid in water to prepare a uniform water dispersion;
(2) adding the butyronitrile latex and the organic peroxide vulcanizing agent in the step (1), and uniformly stirring to obtain mixed slurry;
(3) under the high shearing action of an emulsifying machine, reacting the slurry obtained in the step (2) with calcium hydroxide slurry, and after the reaction is finished, filtering and drying to obtain an intermediate product A;
(4) mixing the intermediate product A obtained in the step (3) in an internal mixer for 5min, discharging the intermediate product A through an open mill, and standing for later use;
(5) measuring a vulcanization curve of the mixed rubber obtained in the step (4) on a disc type vulcanization tester at 170 ℃, determining vulcanization time, vulcanizing on a 25T flat plate vulcanizing machine (the vulcanization temperature is 170 ℃, the vulcanization pressure is 14.5 MPa), and discharging;
(6) and (5) treating the vulcanized rubber obtained in the step (5) by a powder grinding process to obtain the modified powder nitrile-butadiene rubber.
According to the method for preparing the modified powder nitrile rubber, methacrylic acid, terephthalic acid and calcium hydroxide are subjected to acid-base reaction to synthesize calcium methacrylate and calcium terephthalate in situ in the nitrile rubber, and a coordination compound is formed between two organic metal salts through a calcium atom; then under the initiation of organic peroxide, the calcium methacrylate also has grafting reaction with the double bond of the nitrile rubber while generating self-polymerization reaction; in addition, calcium atoms on the surface of the organometallic salt are coordinated to nitrogen atoms in the pendant rubber groups to effect crosslinking. The above factors have the beneficial effects that strong interaction is formed between the organic metal salt and the nitrile rubber, and the organic metal salt can be uniformly dispersed in the polyvinyl chloride and generate strong interaction along with the uniform dispersion between the nitrile rubber and the polyvinyl chloride in the subsequent processing.
Has the advantages that: compared with the traditional powder nitrile rubber, the modified powder nitrile rubber can be uniformly dispersed in a polyvinyl chloride main material, and a hard polyvinyl chloride product modified by the modified powder nitrile rubber not only obtains good toughness, but also well maintains the rigidity and the heat resistance.
Drawings
FIG. 1 is an SEM photograph of the modified nitrile rubber prepared in example 1.
FIG. 2 is an SEM photograph of the modified nitrile rubber prepared in comparative example 1.
FIG. 3 is an SEM picture of the modified nitrile rubber prepared in comparative example 2.
Detailed Description
The invention is further illustrated by the following examples. It should be understood that these examples are illustrative and exemplary of the present invention, and are not intended to limit the scope of the present invention in any way.
Example 1
The invention relates to modified powdered nitrile rubber, which comprises the following components in parts by weight:
100 parts of nitrile-butadiene rubber,
30 parts of calcium polymethacrylate, namely 30 parts of calcium polymethacrylate,
30 parts of calcium terephthalate.
The preparation method of the modified powder nitrile rubber comprises the following process steps:
(1) dispersing methacrylic acid and terephthalic acid in water to prepare a uniform water dispersion;
(2) adding the butyronitrile latex and the organic peroxide vulcanizing agent in the step (1), and uniformly stirring to obtain mixed slurry;
(3) under the high shearing action of an emulsifying machine, reacting the slurry obtained in the step (2) with calcium hydroxide slurry, and after the reaction is finished, filtering and drying to obtain an intermediate product A;
(4) mixing the intermediate product A obtained in the step (3) in an internal mixer for 5min, discharging the intermediate product A through an open mill, and standing for later use;
(5) measuring a vulcanization curve of the mixed rubber obtained in the step (4) on a disc type vulcanization tester at 170 ℃, determining vulcanization time, vulcanizing on a 25T flat plate vulcanizing machine (the vulcanization temperature is 170 ℃, the vulcanization pressure is 14.5 MPa), and discharging;
(6) and (5) treating the vulcanized rubber obtained in the step (5) by a powder grinding process to obtain the modified powder nitrile-butadiene rubber.
Example 2
Example 2 differs from example 1 in that:
the invention relates to modified powdered nitrile rubber, which comprises the following components in parts by weight:
100 parts of nitrile-butadiene rubber,
10 parts of calcium polymethacrylate, wherein the calcium polymethacrylate is,
10 parts of calcium terephthalate.
Example 3
Example 3 differs from example 1 in that:
the invention relates to modified powdered nitrile rubber, which comprises the following components in parts by weight:
100 parts of nitrile-butadiene rubber,
10 parts of calcium polymethacrylate, wherein the calcium polymethacrylate is,
30 parts of calcium terephthalate.
Example 4
Example 4 differs from example 1 in that:
the invention relates to modified powdered nitrile rubber, which comprises the following components in parts by weight:
100 parts of nitrile-butadiene rubber,
30 parts of calcium polymethacrylate, namely 30 parts of calcium polymethacrylate,
10 parts of calcium terephthalate.
Example 5
Example 5 differs from example 1 in that:
the invention relates to modified powdered nitrile rubber, which comprises the following components in parts by weight:
100 parts of nitrile-butadiene rubber,
15 parts of calcium polymethacrylate, wherein the calcium polymethacrylate is a calcium polymethacrylate,
15 parts of calcium terephthalate.
Comparative example 1
Comparative example 1 differs from example 1 in that:
the method for preparing the modified powder nitrile rubber comprises the following process steps: mixing 100 parts of nitrile rubber, 30 parts of calcium methacrylate and 30 parts of calcium terephthalate in a high-speed mixer for 20min to obtain an intermediate product A; mixing the intermediate product A in an internal mixer for 5min, discharging the intermediate product A through an open mill, and standing for later use; measuring a vulcanization curve of the mixed rubber on a disc type vulcanization tester at 170 ℃, determining vulcanization time, vulcanizing on a 25T flat plate vulcanizing machine (the vulcanization temperature is 170 ℃, the vulcanization pressure is 14.5 MPa), and discharging; and finally, carrying out powder grinding process treatment on the vulcanized rubber to obtain the modified powder nitrile rubber.
Comparative example 2
Comparative example 2 differs from example 1 in that:
the method for preparing the modified powder nitrile rubber comprises the following process steps: mixing 100 parts of nitrile rubber, 30 parts of calcium methacrylate and 30 parts of calcium terephthalate in a high-speed mixer for 20min according to parts by weight to obtain the product.
And (3) performance testing:
various types of powdered nitrile rubbers are applied to a polyvinyl chloride formula, and the formula is as follows: 100 parts of PVC (5 type), 10 parts of calcium carbonate, 5 parts of CPE, 6 parts of modified powder nitrile rubber (variants: example 1, comparative example 2 and unmodified nitrile rubber respectively), 1.5 parts of processing aid, 5 parts of environment-friendly stabilizer and 0.5 part of stearic acid.
Weighing and mixing PVC resin, processing aids and other auxiliary material aids according to the formula proportion requirement, adding into a high-speed mixer, and increasing the stirring speed of the mixer from low speed to high speed; when the temperature of the mixed material is gradually increased to 100 ℃, adding calcium carbonate; when the temperature of the mixed materials rises to 100 ℃ again, continuously stirring for 30 s, and then discharging and cooling; cooling to 40-50 deg.C, adding powdered nitrile butadiene rubber, mixing, and storing.
Plasticating the prepared PVC mixed powder into sheets by using an open plasticator; pressing into test sample with certain specification by using a cold and hot press, and testing mechanical and other properties after preparing into a standard sample. The test was carried out according to the national standard and the properties obtained are shown in Table 1.
TABLE 1
From a comparison of the data in the table it can be seen that: the modified powdered nitrile rubber obtained by the invention can improve the toughness of the rigid polyvinyl chloride product at normal temperature and low temperature, and simultaneously, the rigidity and heat resistance of the product are well maintained.
FIGS. 1, 2 and 3 are SEM pictures of the modified nitrile rubbers prepared in example 1, comparative example 1 and comparative example 2, as can be seen by comparison: the interaction between the rubber and the organic metal salt in the modified nitrile rubber prepared by the invention is strongest, and the interaction between the rubber and the organic metal salt is worst when the in-situ modification and the vulcanization crosslinking reaction operation are not carried out.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the foregoing description only for the purpose of illustrating the principles of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the invention as defined by the appended claims, specification, and equivalents thereof.
Claims (1)
1. A modified powder nitrile rubber applied to a hard PVC (polyvinyl chloride) main body material is characterized in that: the modified powder nitrile rubber comprises the following components in parts by weight:
100 parts of nitrile-butadiene rubber,
10-30 parts of calcium polymethacrylate,
10-30 parts of calcium terephthalate;
the preparation method of the modified powder nitrile rubber applied to the hard PVC main body material comprises the following process steps:
(1) dispersing methacrylic acid and terephthalic acid in water to prepare a uniform water dispersion;
(2) adding the butyronitrile latex and the organic peroxide vulcanizing agent in the step (1), and uniformly stirring to obtain mixed slurry;
(3) under the high shearing action of an emulsifying machine, reacting the slurry obtained in the step (2) with calcium hydroxide slurry, and after the reaction is finished, filtering and drying to obtain an intermediate product A;
(4) mixing the intermediate product A obtained in the step (3) in an internal mixer for 5min, discharging the intermediate product A through an open mill, and standing for later use;
(5) measuring a vulcanization curve of the mixed rubber obtained in the step (4) on a disc type vulcanization tester at 170 ℃, determining vulcanization time, vulcanizing on a 25T flat plate vulcanizing machine, and discharging the sheet, wherein the vulcanization temperature is 170 ℃, and the vulcanization pressure is 14.5 MPa;
(6) and (5) treating the vulcanized rubber obtained in the step (5) by a powder grinding process to obtain the modified powder nitrile-butadiene rubber.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003221467A (en) * | 2002-01-30 | 2003-08-05 | Nippon Zeon Co Ltd | Rubber composition, vulcanizable rubber composition, and vulcanized rubber |
| CN103980574A (en) * | 2014-06-05 | 2014-08-13 | 常州市五洲化工有限公司 | Modified nitrile-butadiene rubber (NBR) and preparation method thereof |
| CN105754165A (en) * | 2015-01-26 | 2016-07-13 | 江苏爱特恩东台新材料科技有限公司 | In-situ modification powder rubber and preparation method thereof |
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2018
- 2018-04-18 CN CN201810350866.3A patent/CN108410039B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003221467A (en) * | 2002-01-30 | 2003-08-05 | Nippon Zeon Co Ltd | Rubber composition, vulcanizable rubber composition, and vulcanized rubber |
| CN103980574A (en) * | 2014-06-05 | 2014-08-13 | 常州市五洲化工有限公司 | Modified nitrile-butadiene rubber (NBR) and preparation method thereof |
| CN105754165A (en) * | 2015-01-26 | 2016-07-13 | 江苏爱特恩东台新材料科技有限公司 | In-situ modification powder rubber and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| "不饱和羧酸金属盐在橡胶工业中的应用";赵阳等;《橡胶工业》;20000810;第47卷(第8期);第497-502页 * |
| "甲基丙烯酸原位改性纳米碳酸钙增强丁苯橡胶";马丕明等;《合成橡胶工业》;20071115;第30卷(第6期);第458-462页 * |
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