CN113896964B - Nitrile rubber with low hardness and high acrylonitrile content and preparation method thereof - Google Patents
Nitrile rubber with low hardness and high acrylonitrile content and preparation method thereof Download PDFInfo
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- CN113896964B CN113896964B CN202111446349.4A CN202111446349A CN113896964B CN 113896964 B CN113896964 B CN 113896964B CN 202111446349 A CN202111446349 A CN 202111446349A CN 113896964 B CN113896964 B CN 113896964B
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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
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Abstract
The invention relates to the technical field of rubber manufacturing, and discloses a nitrile rubber with low hardness and high acrylonitrile content, which comprises 40-45 parts of nitrile rubber, 2-3 parts of zinc oxide, 1-2 parts of an anti-aging agent, 5-10 parts of carbon black, 20-25 parts of an inorganic filler, 10-15 parts of a softening agent, 2-5 parts of liquid nitrile rubber, 0.2-0.5 part of sulfur and 1-2 parts of an accelerator. Also disclosed is a method of preparation comprising the steps of: s1: plasticating, namely plasticating the nitrile rubber for 80-100 s, and recording the current value as A1; s2: mixing, namely adding an anti-aging agent and zinc oxide, mixing for 80-100 s, adding carbon black, inorganic filler and 20 parts of softener, wherein the current is more than A1; adding liquid nitrile rubber and 40 parts of softener after 18-25 s, adding the rest softener after the current reaches A1/2, discharging rubber to an open mill when the mixing temperature reaches 85-100 ℃, and then discharging pieces through the open mill; s3: and (4) vulcanizing. The invention can increase the viscosity of the sizing material and improve the air pocket problem.
Description
Technical Field
The invention relates to the technical field of rubber manufacturing, in particular to a low-hardness high-acrylonitrile-content nitrile rubber and a preparation method thereof.
Background
At present, softeners are generally added in the rubber industry to reduce the hardness of rubber, while a large amount of softeners are required to be added to low-hardness rubber, the high-acrylonitrile-content nitrile rubber is a copolymer of acrylonitrile and butadiene, the acrylonitrile content is more than 40%, the polarity of the high-acrylonitrile-content nitrile rubber is high, and the compatibility of the conventional softeners is poor, so that a series of problems can be caused:
1) Mixing is not easy to mix, and the mixing time is prolonged;
2) Poor appearance such as flow marks, air pockets and the like are caused during injection;
3) The softening agent is sprayed during storage or use of the vulcanized product, resulting in an increase in hardness.
Disclosure of Invention
The invention aims to provide the nitrile rubber with low hardness and high acrylonitrile content so as to increase the viscosity of rubber and improve the problem of air pocket.
In order to achieve the purpose, the invention adopts the following technical scheme: the low-hardness high-acrylonitrile-content nitrile rubber comprises, by weight, 40-45 parts of nitrile rubber, 2-3 parts of zinc oxide, 1-2 parts of an anti-aging agent, 5-10 parts of carbon black, 20-25 parts of an inorganic filler, 10-15 parts of a softener, 2-5 parts of liquid nitrile rubber, 0.2-0.5 part of sulfur and 1-2 parts of an accelerator.
Has the advantages that: in the scheme, the elasticity of low-hardness rubber can be improved by adding the liquid nitrile rubber; by adding the inorganic filler, the viscosity of the rubber material can be increased, the problem of air pocket can be improved, and the low-hardness high-acrylonitrile-content nitrile rubber can adapt to an injection process.
Preferably, as an improvement, the nitrile rubber with low hardness and high acrylonitrile content comprises, by weight, 44.7 parts of nitrile rubber, 2.23 parts of zinc oxide, 1.3 parts of anti-aging agent, 8.9 parts of carbon black, 22.3 parts of inorganic filler, 13.4 parts of softener, 4.5 parts of liquid nitrile rubber, 0.4 part of sulfur and 1.5 parts of accelerator.
The proportion in the scheme is a group of proportion commonly used in the preparation process, and the prepared product has better quality.
Preferably, as a modification, the anti-aging agent is anti-aging agent RD or anti-aging agent 4010NA.
The aging inhibitor RD has excellent aging protection effect on heat and oxygen; the anti-aging agent 4010NA has good dispersibility.
Preferably, as an improvement, the carbon black is a fast extrusion carbon black.
The carbon black of the scheme selects the fast extrusion carbon black, which can endow the rubber material with good processability and higher stress at definite elongation, lower elongation and hardness, small heat generation, good heat conductivity and superior high temperature resistance.
Preferably, as an improvement, the inorganic filler is one of white carbon black, kaolin and diatomite or an inorganic filler formed by combining two or more of white carbon black, kaolin and diatomite.
Can adjust according to actual demand in the preparation process in this scheme and choose for use specific inorganic filler, these several kinds of inorganic fillers in this scheme can increase sizing material viscosity, improve the nest gas problem.
Preferably, as an improvement, the softener is a combination of dialkyl ether diester, tributyl citrate, and bis (butoxyethoxyethyl) oxalate in a ratio of 5:3:2.
through the use of high polarity softener in this scheme, can effectually satisfy the compatibility of softener and nitrile rubber, can only adopt one of the three kinds of compositions of this scheme for simplifying the prescription among the prior art at present, the inventor finds in the in-service use of adopting one of the three kinds of compositions when using, the quantity that needs is great, and when adopting a softener, because the quantity is big, and softener itself can not take place chemical reaction, only disperse and get into the rubber the inside, long time can outwards migrate, and lead to producing the softener and appear spun phenomenon, lead to the softener total amount to diminish on the contrary and can not reach better lubricated effect of softening easily, and cause the finished product hardness to rise, the finished product quality has been reduced.
And the softener of the adoption in this scheme adopts three kinds of compositions to use simultaneously, can reduce the quantity of each softener like this, the compatibility of each softener compares in adopting a and the more softener of quantity, and the compatibility of each softener and butadiene-acrylonitrile rubber and other powders can fully be improved in the sharing of three kinds of softeners of this scheme. And three softeners are used together, so that the dispersibility of the softeners can be improved, the spraying condition of the softeners in the using process is reduced, and the hardness of the prepared finished product is prevented from being increased.
Preferably, as an improvement, the promoter is a combination of promoter CZ and promoter TMTD, in a ratio of 1:1.
the promoter CZ is a highly active after-effect promoter, the scorch resistance is excellent, and the reaction rate can be improved by the promoter TMTD and the promoter CZ.
A preparation method of nitrile rubber with low hardness and high acrylonitrile content comprises the following steps:
s1: plasticating, namely plasticating the nitrile rubber for 80-100 s, and recording the current value as A1;
s2: mixing, namely adding the anti-aging agent and zinc oxide, mixing for 80-100 s, then adding carbon black, inorganic filler and 20% of softener, wherein the current is more than A1;
adding liquid nitrile rubber and 40% of softener after 18-25 s, adding the rest softener after the current reaches A1/2, mixing at the temperature of 85-100 ℃ to obtain a semi-finished product, discharging rubber to an open mill, and discharging sheets through the open mill;
s3: and (3) vulcanizing, namely adding sulfur and an accelerator into the semi-finished product prepared in the step (S2) for vulcanization to prepare a finished product.
In the preparation method, in the mixing process, if the current value does not reach the value A1, the powder can be in a loose structure, and because the powder needs to be mixed into the solid rubber material, the powder is mixed only after the current reaches the value A1, so that a relatively uniform state can be formed.
Through the whole softener of disposable addition among the prior art, be difficult for sneaking into when leading to mixing like this easily, mixing time is long, and because the softener is very smooth easily, lead to the softener easily and can not carry out abundant and even mixing with the powder, lead to mixing effect poor, and local saturated phenomenon appears easily, lead to some local softener many, some local softener is few, the place that the softener is many is just easy to spout. And through the control of control reinforced order, add the softener in batches, control softener add time and electric current in this scheme, can effectual improvement softener dispersibility, make the softener can be more abundant and even carry out mixing with rubber and powder, the bad circumstances of appearance such as flow mark, nest gas appear in the product that reduces the later stage preparation.
Detailed Description
The following is further detailed by way of specific embodiments:
example 1
The low-hardness high-acrylonitrile-content nitrile rubber comprises, by weight, 40-45 parts of nitrile rubber, 2-3 parts of zinc oxide, 1-2 parts of an anti-aging agent, 5-10 parts of carbon black, 20-25 parts of an inorganic filler, 10-15 parts of a softener, 2-5 parts of liquid nitrile rubber, 0.2-0.5 part of sulfur and 1-2 parts of an accelerator.
In the preferred embodiment, the rubber composition comprises, by weight, 44.7 parts of nitrile rubber, 2.23 parts of zinc oxide, 1.3 parts of an anti-aging agent, 8.9 parts of carbon black, 22.3 parts of an inorganic filler, 13.4 parts of a softener, 4.5 parts of liquid nitrile rubber, 0.4 part of sulfur and 1.5 parts of an accelerator.
Wherein the nitrile rubber is a copolymer of acrylonitrile and butadiene, and the content of acrylonitrile is more than 40 percent.
The anti-aging agent is anti-aging agent RD or anti-aging agent 4010NA.
The carbon black is a fast-extruding carbon black.
The inorganic filler is one of white carbon black, kaolin and diatomite or is formed by combining two or more of white carbon black, kaolin and diatomite.
The softener in this example is a combination of dialkyl ether diester, tributyl citrate, and bis (butoxyethoxyethyl) oxalate in a ratio of 5:3:2.
the accelerant is a combination of an accelerant CZ and an accelerant TMTD, and the proportion of the accelerant CZ to the accelerant TMTD is 1:1.
the preparation method of the nitrile rubber with low hardness and high acrylonitrile content comprises the following steps:
s1: plasticating, namely plasticating the nitrile rubber, wherein the nitrile rubber is plasticated in a plasticating machine in the embodiment for 80-100 s, preferably 90s in the embodiment, and the recorded current value is A1;
s2: mixing, namely adding the anti-aging agent and the zinc oxide, mixing for 80-100 s, preferably 90s in the embodiment, then adding the carbon black, the inorganic filler and 20% of the softener, wherein the current is more than A1;
after 18 to 25 seconds, preferably 20 seconds in the embodiment, adding liquid nitrile rubber and 40 percent of softener, adding the rest softener after the current reaches A1/2, mixing at the temperature of 85 to 100 ℃ and preferably 90 ℃ in the embodiment to obtain a semi-finished product, discharging rubber to an open mill, and discharging the sheet through the open mill.
S3: and (3) vulcanizing, namely adding sulfur and an accelerator into the semi-finished product prepared in the step (S2) for vulcanization to prepare a finished product.
Examples 2 to 3 and comparative examples 1 and 2
The difference from the example 1 is only the percentage difference of each component, and the specific component percentage is shown in the following table 1:
table 1 shows the percentage of the components in examples 1 to 3 and comparative examples 1 and 2
Comparative example 3:
the difference from the example 1 is that the nitrile rubber, the anti-aging agent, the zinc oxide, the carbon black, the inorganic filler, the softener, the liquid nitrile rubber, the sulfur and the accelerator are mixed and stirred together, then are mixed for 120s to form a mixed rubber, and finally the rubber is discharged and is discharged for sheet discharging. And the softener in this comparative example is one of dialkyl ether diester, tributyl citrate, and bis (butoxyethoxyethyl) oxalate.
The nitrile rubber compound obtained in the examples 1 to 3 and the comparative examples 1 to 3 is taken for performance test, and the test method and the standard are as follows: and (3) testing the rubber elasticity: GB/T1681, viscosity test: GB/T1232, the detection of appearance defective rates such as flow marks, pocks and the like is carried out by manually detecting and judging the appearance. The test results are shown in Table 2.
Table 2 shows the results of the performance tests of examples 1 to 3 and comparative examples 1 to 3.
In conclusion:
1. the viscosity of the rubber compound is the lowest in comparative example 1 without adding an inorganic filler, the viscosity of the rubber compound of example 1, example 2 and example 3 is larger than that of the comparative example, the appearance defect rates of flow marks, pocks and the like of the products of example 1, example 2 and example 3 are all below 10%, and the appearance defect rates of flow marks, pocks and the like of the products of example 1 are the lowest.
In addition, in comparative example 2, no liquid nitrile rubber is added, and the rubber elasticity of the obtained product is the worst, and the rubber elasticity of the products of example 1, example 2 and example 3 is better.
According to the invention, the elasticity of low-hardness rubber can be improved by adding the liquid butyronitrile; by adding the inorganic filler, the viscosity of the rubber material is increased, and the problems of bad appearance such as air pocket and the like are solved.
2. According to the scheme, three softeners are used together, so that the spraying of the softeners can be effectively reduced, and the hardness is prevented from rising; by adding the softening agent in sequence, adding the softening agent in batches and controlling the adding time of the softening agent, the dispersing problem of the softening agent can be effectively improved, so that the appearance defect rate of flow marks, air pockets and the like of products is effectively reduced, and the data in the table 2 also show that the appearance defect rate of the flow marks, the air pockets and the like of the examples 1, 2 and 3 in the invention is obviously lower than that of the comparative examples 1, 2 and 3.
The foregoing is merely an example of the present invention and common general knowledge in the art of designing and/or characterizing particular aspects and/or features is not described in any greater detail herein. It should be noted that, for those skilled in the art, without departing from the technical solution of the present invention, several variations and modifications can be made, and these should also be considered as the protection scope of the present invention, which will not affect the effect of the implementation of the present invention and the practicability of the patent. The scope of the claims of the present application shall be defined by the claims, and the description of the embodiments and the like in the specification shall be used to explain the contents of the claims.
Claims (6)
1. A preparation method of nitrile rubber with low hardness and high acrylonitrile content is characterized by comprising the following steps: according to parts by weight, the flame retardant rubber composition comprises 40-45 parts of nitrile rubber, 2-3 parts of zinc oxide, 1-2 parts of an anti-aging agent, 5-10 parts of carbon black, 20-25 parts of an inorganic filler, 10-15 parts of a softener, 2-5 parts of liquid nitrile rubber, 0.2-0.5 part of sulfur and 1-2 parts of an accelerator; the softener is a combination of dialkyl ether diester, tributyl citrate and bis (butoxy ethoxy ethyl) oxalate, and the proportion is 5:3:2; the preparation method comprises the following steps:
s1: plasticating, namely plasticating the nitrile rubber for 80-100 s, and recording the current value as A1;
s2: mixing, namely adding an anti-aging agent and zinc oxide, mixing for 80-100 s, then adding carbon black, inorganic filler and 20% of softener, wherein the current is more than A1;
adding liquid nitrile rubber and 40% of softener after 18-25 s, adding the rest softener after the current reaches A1/2, mixing at the mixing temperature of 85-100 ℃ to obtain a semi-finished product, discharging rubber to an open mill, and discharging sheets through the open mill;
s3: and (3) vulcanizing, namely adding sulfur and an accelerator into the semi-finished product prepared in the S2 for vulcanization to prepare a finished product.
2. The process for preparing a nitrile rubber with low hardness and high acrylonitrile content as claimed in claim 1, wherein: according to parts by weight, 44.7 parts of nitrile rubber, 2.23 parts of zinc oxide, 1.3 parts of anti-aging agent, 8.9 parts of carbon black, 22.3 parts of inorganic filler, 13.4 parts of softener, 4.5 parts of liquid nitrile rubber, 0.4 part of sulfur and 1.5 parts of accelerator.
3. The method for preparing nitrile rubber with low hardness and high acrylonitrile content as claimed in claim 1, wherein: the anti-aging agent is anti-aging agent RD or anti-aging agent 4010NA.
4. The method for preparing nitrile rubber with low hardness and high acrylonitrile content as claimed in claim 1, wherein: the carbon black is a fast extrusion carbon black.
5. The process for preparing a nitrile rubber with low hardness and high acrylonitrile content as claimed in claim 1, wherein: the inorganic filler is one of white carbon black, kaolin and diatomite or an inorganic filler formed by combining two or more of white carbon black, kaolin and diatomite.
6. The method for preparing nitrile rubber with low hardness and high acrylonitrile content as claimed in claim 1, wherein: the accelerant is a combination of an accelerant CZ and an accelerant TMTD, and the proportion of the accelerant CZ to the accelerant TMTD is 1:1.
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| US6887942B2 (en) * | 2003-04-11 | 2005-05-03 | Chung Shan Instruments Co., Ltd. | Low softening temperature thermal conductive adhesive composition |
| CN103073757B (en) * | 2013-01-28 | 2015-04-01 | 江阴海达橡塑股份有限公司 | Environment-friendly low-condensation-point diesel resistant butadiene-acrylonitrile rubber and preparation method thereof |
| CN104530507A (en) * | 2014-12-23 | 2015-04-22 | 青岛开世密封工业有限公司 | Process method for mixing low-hardness butyronitrile rubber |
| CN107446200B (en) * | 2017-10-12 | 2019-12-06 | 铁岭尔凡橡塑研发有限公司 | Fuel-resistant nitrile rubber material and processing technology thereof |
| CN107814988A (en) * | 2017-11-29 | 2018-03-20 | 安徽微威环保科技有限公司 | A kind of methanol tolerant nitrile rubber and preparation method thereof |
| CN107857908A (en) * | 2017-11-29 | 2018-03-30 | 安徽微威环保科技有限公司 | A kind of methanol tolerant low temperature nitrile rubber and preparation method thereof |
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