CN111154169B - Rubber additive composition, preparation method thereof, rubber formulation and rubber product - Google Patents

Rubber additive composition, preparation method thereof, rubber formulation and rubber product Download PDF

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CN111154169B
CN111154169B CN201911105681.7A CN201911105681A CN111154169B CN 111154169 B CN111154169 B CN 111154169B CN 201911105681 A CN201911105681 A CN 201911105681A CN 111154169 B CN111154169 B CN 111154169B
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rubber
weight
parts
acrylate
additive composition
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CN111154169A (en
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甘仲豪
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Zhuhai Kemaowei New Material Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene
    • 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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C08K5/31—Guanidine; Derivatives thereof
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4

Abstract

The invention provides a rubber additive composition in a granular form, a preparation method thereof, a rubber formulation and a rubber product. The composition comprises: 10.0 to 25.0 wt% of a diacrylate rubber having a molecular structure without a bridge point; and 50.0 to 80.0 wt.% of a rubber co-agent, wherein wt.% is based on the total weight of the rubber additive composition, wherein the diacrylate rubber having an unbridged molecular structure is an ethylene/acrylate elastomer and the rubber co-agent is in powder form. The composition of the invention can improve the storage stability and still keep good production processing performance and product service performance.

Description

Rubber additive composition, preparation method thereof, rubber formulation and rubber product
Technical Field
The invention relates to the field of high molecular polymers, in particular to a rubber additive composition for a rubber preparation, a preparation method thereof, a related rubber preparation and a rubber product.
Background
At present, the industrial and living fields have more and more demands on rubber, in particular special rubber. The preparation and processing of rubber usually contains various additives or rubber auxiliaries. With the development of the rubber additive industry in recent years, one of the important directions for the development of additives for eliminating the problems of chemical smoke and dust pollution in the rubber processing process is product compounding and master batch granulation. The powdered rubber assistant is dispersed in some adhesive system in advance by special means and then granulated to prepare the assistant masterbatch which is used for replacing the traditional powdered assistant, improving the operation environment and improving the product quality, so the granulated assistant can play a role of pre-dispersion, also called pre-dispersion masterbatch particles.
Currently, pre-dispersed masterbatch with rubber additives mainly uses Ethylene Propylene Diene Monomer (EPDM), ethylene-vinyl acetate copolymer (EVA), styrene Butadiene Rubber (SBR), etc. as carriers, such as RHENOGRAN DOTG-70 manufactured and sold by rhine chemical company, which is claimed to be particularly suitable for the processing of acrylate rubbers.
Disclosure of Invention
The inventors have unexpectedly discovered that pre-dispersed masterbatch formulations containing Ethylene Propylene Diene Monomer (EPDM), ethylene Vinyl Acetate (EVA), styrene Butadiene Rubber (SBR), etc. as carriers affect the compatibility and dispersibility of acrylate rubber formulations when used. Therefore, there is a need to develop new pre-dispersed masterbatch particles and related rubber formulations.
In order to solve the above problems, the present invention provides a rubber additive composition using a diacrylate rubber having a molecular structure without bridging points as a carrier, and a method for preparing the same. Related rubber formulations and rubber articles are also provided.
Specifically, the present invention provides:
a rubber additive composition in particulate form comprising:
10.0 to 25.0 wt% of a diacrylate rubber having a molecular structure without a bridge point; and
from 50.0 wt% to 80.0 wt% of a rubber additive, wherein the wt% is based on the total weight of the rubber additive composition,
wherein the binary acrylate rubber with the molecular structure without bridging points is an ethylene/acrylate elastomer, and the rubber auxiliary agent is in a powder form.
Wherein the rubber auxiliary agent is at least one selected from a vulcanization accelerator, a rubber accelerator, a vulcanization activator, an anti-aging agent, a processing auxiliary agent and any combination thereof,
and the vulcanization accelerator is selected from at least one of a guanidine compound, sodium stearate, potassium stearate, zinc dibutyldithiocarbamate, and any combination thereof.
Wherein the rubber additive composition further comprises 5.0 wt% to 15.0 wt% of a processing oil, 0.10 wt% to 5.0 wt% of a filler; and 0.10 to 3.0 wt% of a processing aid.
Wherein the process oil is bis (butoxyethoxyethyl) oxalate, a adipic acid ether-based plasticizer, or any combination thereof;
the filler is selected from at least one of carbon black, white carbon black, calcium carbonate, talc and any combination thereof, and
the processing aid is selected from at least one of primary octadecyl amine, octadecyl phosphate ester, and any combination thereof.
A process for preparing a rubber additive composition in particulate form as claimed in claim 1, comprising the steps of:
putting the binary acrylate rubber with the molecular structure without bridging points and a vulcanization auxiliary agent into an internal mixer or an open mill for mixing for 5-10 minutes to obtain a mixed rubber material, wherein the binary acrylate rubber with the molecular structure without bridging points is an ethylene/acrylate elastomer and the vulcanization auxiliary agent is in a powder form;
feeding the mixed rubber material into a filter, and screening the rubber material through a screen mesh of 80-120 meshes to remove impurities; and
and granulating the filtered rubber material to obtain the rubber additive composition.
Wherein
The rubber auxiliary agent is at least one selected from a vulcanization accelerator, a rubber accelerator, a vulcanization activator, an anti-aging agent, a processing auxiliary agent and any combination thereof, and
the vulcanization accelerator is selected from at least one of di-o-tolylguanidine, sodium stearate, potassium stearate, zinc dibutyldithiocarbamate, and any combination thereof.
Wherein the method further comprises adding at least one selected from the group consisting of a processing oil, a filler, and a processing aid before, during, or after compounding, wherein the processing oil is bis (butoxyethoxyethyl) oxalate, a adipic acid ether-based plasticizer, or any combination thereof.
Wherein the filler is selected from at least one of carbon black, white carbon black, calcium carbonate, talc and any combination thereof, and
wherein the processing aid is selected from at least one of primary octadecyl amine, octadecyl phosphate ester, and any combination thereof.
Wherein the temperature of the mixing is in the range of 60 ℃ to 110 ℃.
Wherein the temperature of granulation is in the range of 40 ℃ to 80 ℃.
A rubber formulation comprising:
an acrylic rubber,
1 to 8 parts by weight of the rubber additive composition described in any of the above with respect to 100 parts by weight of the acrylate rubber;
0 to 10 parts by weight of a vulcanization activator with respect to 100 parts by weight of the acrylate rubber;
5 to 80 parts by weight of a processing oil relative to 100 parts by weight of an acrylate rubber;
0-10 parts by weight of a processing aid, relative to 100 parts by weight of the acrylate rubber;
5 to 100 parts by weight of a filler and
0.5 to 3 parts by weight of stearic acid with respect to 100 parts by weight of the acrylate rubber.
A rubber product is prepared by the crosslinking reaction of the rubber formulation.
The invention has the following advantages and positive effects:
(1) The invention uses the binary acrylate rubber with a non-bridging point molecular structure as the additive composition of the carrier, can improve the storage stability, and still has good production processability and product usability, thereby improving the whole application range of the rubber additive of the acrylate rubber carrier;
(2) The rubber additive composition using the binary acrylate rubber (ACM) with a bridging-point-free molecular structure as a carrier has physical and mechanical properties equivalent to those of a pre-dispersed masterbatch using the traditional Ethylene Propylene Diene Monomer (EPDM) as a carrier; and
(3) Compared with a pre-dispersed masterbatch formulation using Ethylene Propylene Diene Monomer (EPDM) as a carrier, the rubber additive formulation using a binary acrylate rubber with a molecular structure without bridging points as a carrier has higher compatibility and dispersibility with acrylate rubber.
Detailed description of the preferred embodiments
The present invention is further illustrated by the following description of specific embodiments, which are not intended to limit the invention, and various modifications or improvements can be made by those skilled in the art based on the basic idea of the invention, but within the scope of the invention, without departing from the basic idea of the invention.
As used herein, the term "diacrylate rubber having a molecular structure without a bridge point" refers to a diacrylate rubber having no molecular structure that can provide a crosslinking reaction, and a rubber crosslinking reaction can be performed using only peroxide.
In order to improve the storage stability of the pre-dispersed master colloidal particle product and still keep good production processability and product service performance; and further improves the compatibility and dispersibility of the pre-dispersed masterbatch particles with acrylate rubber, the invention provides a novel rubber additive composition which can be prepared into a particle form (namely, a masterbatch form) and contains a binary acrylate rubber with a bridging-point-free molecular structure as a carrier.
Acrylate rubber (ACM) as a novel special rubber has the good characteristics of common rubber, and also has the characteristics of high temperature resistance and oil resistance due to the saturated main chain and the large polar ester group on the side chain, so the ACM is widely applied in industry and life. However, pre-dispersed masterbatch particles used in acrylate rubber formulations have long employed ternary rubbers having bridging points as carriers. The inventors have unexpectedly found that such pre-dispersed masterbatch particles suffer from poor dispersibility and compatibility when used in the processing of acrylate rubbers.
Thus, the present invention provides a novel rubber additive composition that can be prepared in the form of pre-dispersed masterbatch particles and is well suited for the processing and preparation of acrylate rubbers, particularly ECM.
In one aspect according to the invention, a rubber additive composition comprises: 10.0 to 25.0 wt% of a diacrylate rubber having a molecular structure without bridging points and 50.0 to 80.0 wt% of a rubber auxiliary, wherein the wt% is based on the total weight of the rubber additive composition. The binary acrylate rubber with the non-bridging-point molecular structure is an ethylene/acrylate elastomer, and the rubber auxiliary agent is in a powder form.
The rubber auxiliary agents may include rubber accelerators (also referred to as vulcanization accelerators), vulcanization activators, anti-aging agents, processing oils, processing aids and other special functional rubber auxiliary agents, preferably rubber accelerators. The rubber auxiliary agent can be in the form of powder.
In one aspect, the rubber additive composition may further comprise 0.1 wt% to 15.0 wt% of a processing oil. The rubber additive composition may also include 0.10 wt% to 25.0 wt% of a filler. The rubber additive composition may also include 0 wt% to 8.0 wt% of a processing oil.
In a particular embodiment, the diacrylate rubbers having a molecular structure without bridging points are ethylene/acrylate elastomers, with particular preference given to
Figure BDA0002271222390000051
DP or VMX 2122).
Figure BDA0002271222390000052
DP is a binary elastomer of ethylene copolymerized with a methacrylate, having a specific gravity of 1.06 and having a density similar to that of ethylene
Figure BDA0002271222390000053
The terpolymer has excellent comprehensive properties, namely, very good heat resistance, good oil resistance and chemical property, compression deformation resistance and low-temperature flexibility. And
Figure BDA0002271222390000054
the difference between the terpolymers is that,
Figure BDA0002271222390000055
the DP binary copolymer is compounded and vulcanized by adopting a peroxide system, so that the storage stability of the product is very good.
In particular embodiments, the process oil may be selected from any process oil known in the art. In more specific embodiments, the processing oil is at least one selected from the group consisting of bis (butoxyethoxyethyl) oxalate (TP-95), adipic acid ether-based plasticizer (RS-107), or any combination thereof.
The plasticizer TP-95 has low volatility, is easy to disperse and does not reduce the physical properties of the rubber compound, so that the plasticizer TP-95 can be kept effective in a wide temperature range, and simultaneously provides excellent plasticizing effect without seriously damaging the physical properties of the compound.
In particular embodiments, the vulcanization accelerator may be selected from any vulcanization accelerator known in the art. In a more specific embodiment, the vulcanization accelerator is selected from the group consisting of guanidine compounds, sodium stearate, potassium stearate, zinc dibutyldithiocarbamate, and any combination thereof, more preferably di-o-tolylguanidine (DOTG), o-tolylbiguanidine, and/or diphenylguanidine. These vulcanization accelerators may be in powder form and are therefore preferably processed into predispersed masterbatch to reduce dust contamination during rubber processing.
In particular embodiments, the filler may be selected from any filler known in the art. In a more specific embodiment, the filler is selected from at least one of carbon black, white carbon black, calcium carbonate, talc, and any combination thereof, more preferably carbon black.
In particular embodiments, the processing aid may be selected from any processing aid known in the art. In a more specific embodiment, the processing aid is selected from at least one of a primary octadecyl amine, an octadecyl phosphate ester, and any combination thereof. In an even more specific embodiment, the processing aids are primary octadecyl amines and octadecyl phosphate esters. For example, useful processing aids include DISMO 18D, DISMO 1822, DISMO VAM, and the like, available from Kyoho rubber and plastic materials, inc.
According to embodiments of the present invention, the rubber additive composition can be prepared in the form of a pre-dispersed masterbatch. The formula of the pre-dispersed masterbatch comprises powder (such as a vulcanization accelerator), processing oil, a processing aid, a filler, a rubber carrier and the like, wherein the powder is a main component of the masterbatch, the processing oil is used for wetting the surface of the powder, the processing aid is used for improving the dispersion effect of a chemical aid in rubber, the filler reduces the volume cost, and the rubber carrier plays a role in bonding in the formula of the pre-dispersed masterbatch.
In a particular embodiment, the rubber additive composition comprises: 10.0 to 25.0% by weight of
Figure BDA0002271222390000062
DP;0 to 15.0 wt% of TP-95 (RS-107); 50.0 to 80.0 parts by weight of DOTG;0 to 25.0% by weight of carbon black N774;0 to 8.0 wt% primary octadecyl amine and 0 to 8.0 wt% octadecyl phosphate JH-E1800.
In a more specific embodiment, the rubber additive composition may comprise: 17.5% by weight of
Figure BDA0002271222390000061
DP;8.85 wt% TP-95 (RS-107); 71.5 wt.% DOTG; 0.15% by weight of carbon black N774; 1.0% by weight of primary octadecyl amine and 1.0% by weight of octadecyl phosphate.
The rubber additive composition according to the first aspect of the invention has improved storage stability, and still maintains good production processability and product usability, thereby improving the overall application range of the rubber additive.
In another aspect according to the present invention, a method of preparing a rubber additive composition comprises the steps of:
(a) Mixing binary acrylate rubber with a non-bridging-point molecular structure with a vulcanization aid to obtain a rubber material;
filtering the size; and
(b) Filtering the size;
(c) The filtered compound is pelletized to obtain a rubber additive composition (which may also be referred to as a predispersed masterbatch).
Optionally, the method of preparing the rubber additive composition further comprises adding a processing oil before, during, or after compounding.
Optionally, the method of preparing the rubber additive composition further comprises adding a filler before, during, or after mixing;
optionally, the method of preparing the rubber additive composition further comprises adding a processing aid before, during, or after mixing.
Optionally, the process oil is bis (butoxyethoxyethyl) oxalate, a adipic acid ether-based plasticizer, or any combination thereof.
Optionally, the filler is selected from at least one of carbon black, white carbon black, calcium carbonate, talc, and any combination thereof.
Optionally, the processing aid is selected from at least one of a primary octadecyl amine, an octadecyl phosphate ester, and any combination thereof.
The binary acrylate rubber with a molecular structure without bridging points, the processing oil, the vulcanization accelerator, the filler and the processing aid are as described above.
The above steps are described in more detail below.
In step (a), the diacrylate rubber having a molecular structure without a bridge point and the processing aid (when present, further including processing oil, vulcanization accelerator and/or filler) each in an amount within the above-mentioned range are charged into an internal mixer or an open mill, and kneaded at a temperature of 60 to 90 ℃ for 5 to 10 minutes at a rotation speed of 60 to 70 revolutions per minute to obtain a rubber compound. The internal mixer or open mill may be an internal mixer or open mill conventionally known in the art.
In step (b), the rubber material obtained in step (a) is fed to a filter to remove impurities, wherein the mesh number of the screen of the filter is 60-100 meshes to remove impurities.
In step (c), the filtered compound is fed to a granulator to obtain the rubber additive composition in the form of granules. The temperature in the granulator is in the range of 60 to 80. In a particular embodiment, the granulator is, for example, an extruder.
The formula of the rubber additive composition using the binary acrylate rubber prepared by the method as a carrier meets the technical indexes of standard qualified products shown in the following table 1:
TABLE 1 technical index of qualified rubber additive composition formulation using a diacrylate rubber as a carrier
Index name Qualified product
Appearance (visual inspection) White to off-white particles
Specific gravity g/cm 3 1.05±0.1
Mooney ML (1 + 4), 50 DEG C 50±20
The present invention will be further described with reference to specific examples.
Example 1
According to the percentage contents shown in example 1 of the following table 2, the
Figure BDA0002271222390000081
DP, rubber accelerator DOTG and plasticizer TP-95, carbon black N774, primary octadecyl amine and octadecyl phosphate were charged into an internal mixer (model HX-8101-5, available from Honghianxiang, dongguan) and mixed at a temperature of 80 ℃ and a rotational speed of 70 revolutions per minute for 10 minutes to obtain a rubber compound. The obtained rubber material is fed into a filter with the mesh number of a screen being 100 meshes, and the rubber material is filtered through a screen with 100 meshes to remove impurities mixed in the accelerator powder. Feeding the filtered rubber material into an extruder and granulating at the temperature of 80 ℃ to obtain pre-dispersed mother materialGranule 1.
Example 2
According to the percentage contents shown in example 2 of the following table 2, the
Figure BDA0002271222390000082
DP, rubber accelerator DOTG and plasticizer TP-95, carbon black N774, primary octadecyl amine and octadecyl phosphate were put into an internal mixer (model HX-8101-5, obtained from Hongxiangxiang company, imperial, china) and mixed for 10 minutes at a temperature of 80 ℃ and a rotation speed of 70 revolutions per minute to obtain a rubber compound. The obtained rubber material is fed into a filter with the mesh number of a screen being 100 meshes, and the rubber material is filtered through a screen with 100 meshes to remove impurities mixed in the accelerator powder. The filtered gum mass was fed into an extruder and granulated at a temperature of 80 ℃ to predisperse masterbatch 2.
Example 3
According to the percentage contents shown in example 3 of the following table 2, the
Figure BDA0002271222390000083
DP, rubber accelerator DOTG and plasticizer TP-95, carbon black N774, primary octadecyl amine and octadecyl phosphate were put into an internal mixer (model HX-8101-5, obtained from Hongxiangxiang company, imperial, china) and mixed for 10 minutes at a temperature of 80 ℃ and a rotation speed of 70 revolutions per minute to obtain a rubber compound. The obtained rubber material is fed to a filter with the mesh number of 100 meshes, and the rubber material is filtered through a 100-mesh screen to remove impurities in the accelerator powder. The filtered compound was fed into an extruder and granulated at a temperature of 80 ℃ to obtain predispersed masterbatch 3.
Example 4
According to the percentage contents shown in example 4 of the following table 2, the
Figure BDA0002271222390000091
DP, rubber accelerator DOTG and plasticizer TP-95, carbon black N774, primary octadecyl amine and octadecyl phosphate were put into an internal mixer (model HX-8101-5, obtained from Hongxiangxiang company, imperial, china) and mixed for 10 minutes at a temperature of 80 ℃ and a rotation speed of 70 revolutions per minute to obtain a rubber compound. Blanking the obtained rubber material to a filter with the mesh number of a screen being 100 meshes, and sieving the rubber material by a screen with 100 meshes to obtain the rubber materialRemoving impurities in the promoter powder. The filtered rubber material is put into an extruder and granulated at a temperature of 80 ℃ to obtain the predispersed masterbatch 4.
Example 5
According to the percentage content shown in example 5 of the following table 2, the
Figure BDA0002271222390000092
DP, rubber accelerator DOTG and plasticizer TP-95, carbon black N774, primary octadecyl amine and octadecyl phosphate were put into an internal mixer (model HX-8101-5, obtained from Hongxiangxiang company, imperial, china) and mixed for 10 minutes at a temperature of 80 ℃ and a rotation speed of 70 revolutions per minute to obtain a rubber compound. The obtained rubber material is fed into a filter with the mesh number of a screen being 100 meshes, and the rubber material is filtered through a screen with 100 meshes to remove impurities mixed in the accelerator powder. The filtered rubber material was put into an extruder and granulated at a temperature of 80 ℃ to obtain predispersed masterbatch 5.
Example 6
According to the percentage contents shown in example 6 of the following table 2, the
Figure BDA0002271222390000093
DP, rubber accelerator DOTG, plasticizer TP-95, carbon black N774, primary octadecyl amine and octadecyl phosphate were put into an internal mixer (model HX-8101-5, obtained from imperial China Hongxiang Co., ltd.) and mixed at 80 ℃ and 70 rpm for 10 minutes to obtain a rubber compound. The obtained rubber material is fed into a filter with the mesh number of a screen being 100 meshes, and the rubber material is filtered through a screen with 100 meshes to remove impurities mixed in the accelerator powder. The filtered compound was fed into an extruder and granulated at a temperature of 80 ℃ to obtain predispersed masterbatch 6.
Example 7
According to the percentage contents shown in example 7 of the following table 2, the
Figure BDA0002271222390000094
DP, rubber accelerator DOTG and plasticizer TP-95, carbon black N774, primary octadecyl amine and octadecyl phosphate were charged into an internal mixer (model HX-8101-5, available from Honghianxiang, dongguan) at a temperature of 80 deg.C,And mixing for 10 minutes at a rotating speed of 70 revolutions per minute to obtain a sizing material. The obtained rubber material is fed to a filter with the mesh number of 100 meshes, and the rubber material is filtered through a 100-mesh screen to remove impurities in the accelerator powder. The filtered gum material was fed into an extruder and granulated at a temperature of 80 ℃ to obtain predispersed masterbatch 7.
In the examples of Table 2, the weight percentages of the components are
Figure BDA0002271222390000101
Test example
The dispersibility of the predispersed masterbatch 1-7 was tested according to the extrusion filtration dispersibility test. The predispersed rubber masterbatch of examples 1-7 was added to the dispersion formulation shown in table 3 below to prepare a rubber compound. Then, the filter screen was observed for residual impurities by extrusion filtering a 150-mesh screen. The results of the dispersibility measurements are shown in Table 4 below.
Then, the predispersed rubber master batch in examples 1 to 7 was added to the acrylate rubber Vamac G in the formulation shown in table 5 below to prepare a rubber compound. The vulcanization was then carried out in an MDR2000 vulcanizer. The results of the vulcanization test are shown in Table 6 below. The resulting vulcanized rubber was tested for physical properties. The results are shown in Table 7.
TABLE 3 rubber application test formulation
Figure BDA0002271222390000111
TABLE 4 results of vulcanization and physical property test of the rubber obtained from each of the above formulations
Figure BDA0002271222390000112
TABLE 5 rubber application test formulation
Figure BDA0002271222390000113
Figure BDA0002271222390000121
The pre-dispersed master batch is prepared by adding 4.17 at 70% as reference, and adding the same effective content by converting the rest according to content ratio
TABLE 6 vulcanization test results for rubber obtained from each of the above formulations
Figure BDA0002271222390000122
TABLE 7 results of physical Properties test of the rubbers obtained from the above-mentioned respective formulations
Figure BDA0002271222390000131
Table 7 shows that formula 1 contains too much rubber auxiliary agent, so the dispersibility is poor, the performance test data of the rubber formula is unstable, and the data deviation of three tests is large. Formulation 6 also resulted in unstable performance test data due to the lower amount of the diacrylate rubber. Formulation 7, due to the use of EPDM rather than the diacrylate rubber Vamac G, exhibited poor dispersion, resulting in unstable performance test data.
In contrast, formulations 2 to 5 according to the invention have good dispersion stability and the performance test data are also more stable.
In the above table, the description of the various substances and instruments is as follows:
acrylate rubber Vamac G: from DuPont, USA
Stearic acid: from Fine chemical Co Ltd of corridor, peng color
Processing aid DISMO 18D: from Zhuhaike metallocene rubber and Plastic materials Ltd
Processing aid DISMO VAM: from Zhuhaike metallocene rubber and Plastic materials Ltd
Carbon black N550: from Jiangsu Ming Qian trading Co Ltd
Processing oil: TP95 available from Rohm and Haas company, USA
Vulcanizing agent Diac-1 (70%): from Zhuhai Polysynthesis materials Ltd
Rubber accelerator DOTG (70%): from Sanmenhuamai chemical products Co Ltd
ACM vector: self-contained articles
EPDM support: self-contained articles
In addition, the tests for the respective properties shown in table 6 employ test methods known in the art, as shown in table 8 below:
TABLE 8
Figure BDA0002271222390000141
From the above results, it can be seen that compared with the product obtained by mixing the pre-dispersed masterbatch particle with the traditional Ethylene Propylene Diene Monomer (EPDM) as the carrier and the acrylate rubber, the pre-dispersed masterbatch particle with the binary acrylate rubber as the carrier has higher compatibility and dispersibility with the acrylate rubber, and the physical properties are still not substantially damaged.
Therefore, the invention can be applied to the field of rubber industrial products.
It should be noted that the above-mentioned preferred embodiments only illustrate the present invention, and the scope of the claims of the present invention is not limited thereto, so that equivalent changes made by using the contents of the description and the accompanying drawings of the present invention should be included in the scope of the claims of the present invention without departing from the spirit of the present invention.

Claims (5)

1. A rubber additive composition in particulate form comprising:
17.5% by weight of a diacrylate rubber having a molecular structure without bridge points
Figure FDA0004005461350000011
DP；
8.85% by weight of bis (butoxyethoxyethyl) oxalate TP-95;
71.5% by weight of di-o-tolylguanidine DOTG;
0.15% by weight of carbon black N774;
1.0 wt.% primary octadecyl amine; and
1.0 wt.% of octadecyl phosphate;
wherein the weight percents are based on the total weight of the rubber additive composition,
wherein the diacrylate rubber having a molecular structure without bridging points is a binary ethylene/acrylate elastomer having no molecular structure that can provide a crosslinking reaction, the rubber crosslinking reaction can be performed using only peroxide, and the di-o-tolylguanidine DOTG is in the form of powder.
2. A process for preparing a rubber additive composition in particulate form according to claim 1 comprising the steps of:
the binary acrylate rubber with a molecular structure without bridging points
Figure FDA0004005461350000012
DP and a vulcanization aid are thrown into an internal mixer or an open mill for mixing for 5-10 minutes to obtain a mixed rubber material, wherein the binary acrylate rubber with the molecular structure without bridging points has no molecular structure capable of providing a crosslinking reaction, the binary ethylene/acrylate elastomer can only use peroxide for the rubber crosslinking reaction, and the vulcanization aid is in a powder form;
feeding the mixed rubber material into a filter, and screening the rubber material through a screen of 80-120 meshes to remove impurities; and
pelletizing the filtered compound to obtain a rubber additive composition, wherein the vulcanization aid is selected from the group consisting of di-o-tolylguanidine DOTG, and further comprising adding di (butoxyethoxyethyl) oxalate, carbon black N774, primary octadecylamine before, during, or after mixing; and octadecyl phosphate.
3. The method of claim 2, wherein
The temperature of the mixing is in the range of 60 ℃ to 110 ℃, and
the temperature of granulation is in the range of 40 ℃ to 80 ℃.
4. A rubber formulation comprising:
an acrylic rubber,
1 to 8 parts by weight of the rubber additive composition of claim 1, relative to 100 parts by weight of the acrylate rubber;
0 to 10 parts by weight of a vulcanization activator with respect to 100 parts by weight of the acrylate rubber;
5 to 80 parts by weight of a processing oil relative to 100 parts by weight of an acrylate rubber;
0 to 10 parts by weight of a processing aid relative to 100 parts by weight of the acrylate rubber;
5 to 100 parts by weight of a filler relative to 100 parts by weight of the acrylate rubber and 0.5 to 3 parts by weight of stearic acid relative to 100 parts by weight of the acrylate rubber.
5. A rubber article prepared by crosslinking the rubber formulation of claim 4.
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