CN105295275B - A kind of pre-dispersed masterbatch particles of esters of acrylic acid rubber accelerator and preparation method thereof - Google Patents
A kind of pre-dispersed masterbatch particles of esters of acrylic acid rubber accelerator and preparation method thereof Download PDFInfo
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- CN105295275B CN105295275B CN201510672507.6A CN201510672507A CN105295275B CN 105295275 B CN105295275 B CN 105295275B CN 201510672507 A CN201510672507 A CN 201510672507A CN 105295275 B CN105295275 B CN 105295275B
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Abstract
The invention discloses a kind of pre-dispersed masterbatch particles of esters of acrylic acid rubber accelerator and preparation method thereof.The pre-dispersed masterbatch particles include the component of following parts by weight：20~40 parts of acrylic polymer carrier, 10~25 parts of dialkyl dithiophosphate, 20~40 parts of diamine compounds, 20~40 parts of inorganic filler, 1~10 part of operation oil.When the pre-dispersed masterbatch particles are used for the esters of acrylic acid vulcanization of rubber, compared with existing esters of acrylic acid rubber accelerator, it can not only keep the physical characteristic of esters of acrylic acid rubber after vulcanizing, and safety and environmental protection, easily dispersion, curing efficiency can be effectively improved, optimization time of scorch, do not generate bloom phenomenon, improve the low compressive deformation and ageing-resistant performance of rubber.
Description
Technical field
The invention belongs to rubber chemicals technical fields, and in particular to a kind of pre-dispersed rubber master batch of esters of acrylic acid rubber accelerator
Grain and preparation method thereof.
Background technology
It using acrylate or methacrylate is monomer through being copolymerized the elastomer formed, master that esters of acrylic acid rubber, which is,
Chain is saturated carbon chains, and side group is polar ester groups, which assigns its many excellent performance, such as heat-resisting, resistance to old
Change, oil resistant, resistance to ozone, uvioresistant etc., mechanical property and processing performance are better than fluorubber and silicon rubber, heat-resisting, resistance to ag(e)ing
It is better than nitrile rubber with oil resistivity.Therefore, esters of acrylic acid rubber is widely used in various high temperature, resistance to oil environment, has become
A kind of high-performance rubber material for focusing on to develop and promote for auto industry in recent years.
But the vulcanization characteristics of esters of acrylic acid rubber is relatively low, needs efficient vulcanizing system, to substitute those for biography
The system vulcanization of rubber and peroxidating system.At present, frequently with diphenylguanidine, two adjacent first in the vulcanizing system of esters of acrylic acid rubber
Benzene guanidine and its derivative are as vulcanization accelerator, but this kind of product can when other vulcanizing agents are used together in sulfidation
Generate potential carcinogen matter ortho-aminotoluene.
In addition, in existing rubber processing treatment process, some rubber chemicals, the powdery for being especially difficult to disperse helps
There is the problem of being difficult to disperse, being difficult to be mixed into rubber or be difficult to measure in agent, inorganic matter etc..It is quick with auto industry
Development, either to the physicochemical property of raw materials for rubber industry still to the rapid processing characteristic and quality stability of raw material
All put forward higher requirements.In order to reach requirement of the modern rubber processing industry to high quality and high yield, it may be difficult to disperse, be difficult to
The rubber chemicals measured are mixed into or are difficult to easily to disperse, be easily mixed into, easily measure product to be very must by pre-processing to be processed into
It wants.The method of generally use is that this kind of rubber chemicals are prepared into pre-dispersed masterbatch particles at present.Pre-dispersed masterbatch particles are by this
Class rubber chemicals and a small amount of rubber and a small amount of softening oil and dispersant etc. make rubber by mixing, disperseing and prilling
Auxiliary agent is pre-dispersed in the formation pre-dispersed rubber master batch granule product of rubber chemicals in rubber.This pre-dispersed masterbatch particles are used for rubber
Production, not only reduces dust pollution, improves metering accuracy and convenience, it is often more important that ensure that auxiliary agent is mixed into speed
On the other hand degree, rate of dispersion and dispersing uniformity also can effectively reduce mixing energy consumption, effects of energy saving and emission reduction is notable.
Invention content
For the above-mentioned state of the art, the present invention is intended to provide a kind of pre-dispersed masterbatch particles of esters of acrylic acid rubber accelerator,
There is safety and environmental protection, be easily dispersed in esters of acrylic acid rubber, and curing efficiency is high.
In order to realize above-mentioned technical purpose, technical solution provided by the invention is：A kind of esters of acrylic acid rubber accelerator
Pre-dispersed masterbatch particles in terms of parts by weight, include the component of following parts by weight：
The acrylic polymer is as carrier, including but not limited to acrylic rubber, ethylene-acrylate rubber
One kind in glue, ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer etc. or
Two or more mixtures.
The dialkyl dithiophosphate includes the dialkyl dithiophosphate that atomic number of alkyl carbon is 4~18.
Metal ion in the dialkyl dithiophosphate can be one kind in the metal ions such as zinc, calcium, molybdenum, bismuth, magnesium or
Two or more mixing.The dialkyl dithiophosphate can be specifically zinc dialkyl dithiophosphate, dialkyl group two
One kind in D2EHDTPA calcium, molybdenum dialkyl-dithiophosphate, dialkyl dithiophosphoric acid bismuth, dialkyl dithiophosphoric acid magnesium etc.
Or two or more mixture.
The diamine compounds refer to the compound containing diazabicyclo structure, including but not limited to 2,5- phenodiazines
Miscellaneous bicyclic [2.2.1] heptane, 3,7- diazabicyclos [3.3.0] octane, 3,8- diazabicyclos [3.2.1] octane, 1,4- bis-
Azabicyclo [3.2.2] nonane, 1,4- azabicyclos [4.3.0] nonane, 2,8- diazabicyclos [4.3.0] nonane, 6,8- bis-
Azabicyclo [3.2.2] nonane, 1,4- diazabicyclos [4.3.1] decane, 11 carbon -7- of 1,8- diazabicyclos [5.4.0]
The mixture of one or more of alkene.
The inorganic filler is included in white carbon, calcium carbonate, talcum powder, clay, magnesium powder, carbon black, aluminium hydroxide etc.
One or more kinds of mixtures.
The operation oil is used to improve the processing performance of sizing material, including but not limited to paraffinic, cycloalkane, fragrance
The mixture of one or more of the greases such as hydro carbons.
Preferably, the pre-dispersed masterbatch particles of esters of acrylic acid rubber accelerator of the present invention further include interleaving agent, for preventing
The mutual bonding of pre-dispersed rubber master batch intergranular.The interleaving agent is unlimited, including one in talcum powder, calcium carbonate, starch, clay etc.
Kind or two or more mixtures.As further preferred, the parts by weight of the interleaving agent are 0.1~0.5 part.
As a kind of way of realization, the total weight of the pre-dispersed masterbatch particles of esters of acrylic acid rubber accelerator of the present invention is with 100
Part meter includes the component of following parts by weight：
The present invention also provides a kind of method for preparing the above-mentioned pre-dispersed masterbatch particles of esters of acrylic acid rubber accelerator, including
Following steps：
(1) acrylic polymer carrier is added in by the parts by weight and is kneaded into mixer；
Preferably, in the step (1), the processing temperature is 30~80 DEG C, and rotor speed is 20~80r/min；
Preferably, in the step (1), the mixing time is 1~15min, further preferably 5~8min；
(2) inorganic filler, operation oil are added in into the mixer in step (1) and carried out respectively by the parts by weight
It is kneaded；
Preferably, in the step (2), the processing temperature is 30~80 DEG C, rotor speed is 20~80r/min；
Preferably, in the step (2), the mixing time is 1~15min, further preferably 5~8min；
(3) dialkyl dithiophosphate and diamine compounds are added in step respectively by the parts by weight
(2) it is kneaded in the mixer in, sizing material is made；
Preferably, in the step (3), the processing temperature is 50~80 DEG C, rotor speed is 50~80r/min；
Preferably, in the step (3), the mixing time is 1~30min, further preferably 5~15min；
Preferably, in the step (3), dialkyl dithiophosphate and diamine compounds are added in several times to step
Suddenly the mixer in (2)；
(4) sizing material after being kneaded in step (3) is added in and is squeezed out, be granulated into single screw extrusion machine, be made pre- point
Dissipate masterbatch particles；
Preferably, in the step (4), the processing temperature of the single screw extrusion machine is 50~80 DEG C, screw speed is
30~60r/min；
Preferably, in the step (4), a diameter of 5~20mm of the pre-dispersed masterbatch particles, length is 5~25mm；
In the step (4), occur mutually to bond in order to prevent between pre-dispersed masterbatch particles obtained, preferably, making
After obtaining the pre-dispersed masterbatch particles, a certain amount of interleaving agent is added for preventing pre-dispersed masterbatch particles from bonding.It is described every
It is unlimited from agent, include the mixture of one or more of talcum powder, calcium carbonate, starch, clay etc..As further excellent
Choosing, the parts by weight of the interleaving agent are 0.1~0.5 part.
Compared with prior art, the invention has the advantages that：
(1) esters of acrylic acid rubber accelerator of the invention is using acrylic polymer as carrier, including two
Alkyl dithiophosphoric acid salt and diamine compounds, the two synergistic effect are and existing during for the esters of acrylic acid vulcanization of rubber
Esters of acrylic acid rubber accelerator is compared, and can not only keep the physical characteristic of esters of acrylic acid rubber after vulcanization, and can
The curing efficiency, optimization time of scorch, rubber no blooming of esters of acrylic acid rubber are effectively improved, improves rubber
Low compressive deformation and ageing-resistant performance；Therefore alternative existing esters of acrylic acid thiofide, such as diphenylguanidine, two
Adjacent toluene guanidine and its derivative etc.；
(2) ingredients such as ortho-aminotoluene are not detected in esters of acrylic acid rubber accelerator of the invention, in sulfidation with
The ingredients such as ortho-aminotoluene are not generated when other vulcanizing agents are used together, it is thus eliminated that carcinogenic risk, safety and environmental protection；
(3) esters of acrylic acid rubber accelerator of the invention solves accelerating agent mixed using pre-dispersed masterbatch particles form
The problems such as quality and energy consumption so as to bring being hard to be uniformly dispersed in rubber in refining and sulfidation.
Description of the drawings
Fig. 1 is the curing curve of the ethylene-acrylate rubber under Elastomers with Different Curing Systems in the embodiment of the present invention 1；
Fig. 2 is the curing curve of the ethylene-acrylate rubber under Elastomers with Different Curing Systems in the embodiment of the present invention 2.
Specific embodiment
Embodiment is described in further detail the present invention below in conjunction with the accompanying drawings, it should be pointed out that implementation as described below
Example is intended to convenient for the understanding of the present invention, and does not play any restriction effect to it.
Embodiment 1：
The pre-dispersed masterbatch particles ACT-70-1 of esters of acrylic acid rubber accelerator, by total weight for based on 100 parts, each component and
Its parts by weight is as follows：
28 parts of acrylic rubber, 19 parts of diisobutyl D2EHDTPA zinc, 2,5- diazabicyclos [2.2.1] heptane 23
Part, 24 parts of white carbon, 5.7 parts of paraffin type process oil, 0.3 part of talcum powder.
The preparation method of the above-mentioned pre-dispersed masterbatch particles of acrylic rubber accelerating agent, includes the following steps：
(1) acrylic rubber is added in by above-mentioned parts by weight into mixer, is 50 DEG C, rotor speed in processing temperature
Under conditions of 60r/min, it is kneaded 6min；
(2) white carbon, paraffin type process oil are added in the mixer in step (1) respectively by above-mentioned parts by weight
In, under conditions of processing temperature is 50 DEG C, rotor speed is 60r/min, continue to be kneaded 6min；
(3) by above-mentioned parts by weight respectively by diisobutyl D2EHDTPA zinc and 2,5- diazabicyclos [2.2.1] heptane
It is added in several times into the mixer in step (2), under conditions of processing temperature is 70 DEG C, rotor speed is 70r/min, after
It is continuous to be kneaded 12min, sizing material is made；
(4) sizing material after being kneaded in step (3) is added in into single screw extrusion machine, sets processing temperature as 60 DEG C, spiral shell
Bar rotating speed is 40r/min, is squeezed out, is granulated, and the particle that diameter and length are about 6mm is made, then adds above-mentioned parts by weight
Several talcum powder interleaving agents is to get the pre-dispersed rubber master batch granule product ACT-70-1 of esters of acrylic acid rubber accelerator.
The pre-dispersed masterbatch particles ACT-70-1 of esters of acrylic acid rubber accelerator obtained above is subjected to in-vehicle air and vehicle
Inside gadget material organic volatile analyte detection (VOC), test result are：Ortho-aminotoluene ingredient is not detected.
In order to investigate the pre-dispersed masterbatch particles ACT-70-1 of esters of acrylic acid rubber accelerator obtained above to ethylene, propylene
The influence of acid esters rubber (AEM) vulcanizing system rheological property and physical property, using accelerating agent di-o-tolylguanidine (DOTG) conduct
Control carries out vulcanizing system design according to each group distribution ratio in table 1.
The vulcanizing system formula of 1 ethylene-acrylate rubber of table
Fig. 1 and table 2 are respectively 1#Vulcanizing system and 2#The curing curve and rheology of ethylene-acrylate rubber under vulcanizing system
Parameter.From Fig. 1 and table 2 as can be seen that the accelerating agent masterbatch particles ACT-70-1 can not only substitute DOTG completely, but also
The coke burning performance and curing efficiency of vulcanizing system can be improved.
The rheological parameter (vulcanization characteristics parameter) of ethylene-acrylate rubber under 2 Elastomers with Different Curing Systems of table
| Performance parameter | 1# | 2# |
| Mooney viscosity, ML (1+4), 100 DEG C | 64 | 61 |
| TS1(s) | 46 | 45 |
| TS2(s) | 75 | 69 |
| TC10(s) | 40 | 40 |
| TC90(s) | 574 | 543 |
| ML(dN·m) | 1.97 | 2.28 |
| MH(dN·m) | 9.47 | 9.72 |
Table 3 is 1#Vulcanizing system and 2#The physical property of the lower ethylene-acrylate rubber of vulcanizing system.It can be with from table 3
Find out, DOTG is substituted using ACT-70-1, ethylene-acrylate rubber can keep all physical characteristics, wherein compressive deformation
It is significantly improved.
The physical property of ethylene-acrylate rubber under 3 Elastomers with Different Curing Systems of table
| Performance parameter | 1# | 2# |
| Hardness | 74 | 76 |
| Elongation at break (%) | 273 | 229 |
| Tension (MPa) | 15.1 | 15.3 |
| Tearing strength (MPa) | 18.1 | 17.2 |
| Compressive deformation (%) | 8.9 | 11.4 |
Embodiment 2
The pre-dispersed masterbatch particles ACT-70-2 of esters of acrylic acid rubber accelerator, by total weight for based on 100 parts, each component and
Its parts by weight is as follows：
24 parts of ethylene methyl acrylate copolymer, 23 parts of isobutyl group octylsulfo bismuth phosphate, 3,8- diazabicyclos
23 parts of [3.2.1] octane, 20 parts of calcium carbonate, aromatic hydrocarbons generic operation oily 9.6 parts, 0.4 part of starch.
The preparation method of the above-mentioned pre-dispersed masterbatch particles of esters of acrylic acid rubber accelerator, includes the following steps：
(1) ethylene acrylate copolymer is added in by above-mentioned parts by weight into mixer, is 55 DEG C, turns in processing temperature
Under conditions of rotor speed is 50r/min, it is kneaded 5min；
(2) calcium carbonate, aromatic hydrocarbons generic operation oil are added in into the mixer in step (1) respectively by above-mentioned parts by weight,
Under conditions of processing temperature is 60 DEG C, rotor speed is 60r/min, continue to be kneaded 8min；
(3) it is respectively that isobutyl group octylsulfo bismuth phosphate and 3,8- diazabicyclos [3.2.1] is pungent by above-mentioned parts by weight
Alkane is added in several times into the mixer in step (1), under conditions of processing temperature is 50 DEG C, rotor speed is 60r/min,
Continue to be kneaded 9min, sizing material is made；
(4) sizing material after being kneaded in step (3) is added in into single screw extrusion machine, sets processing temperature as 50 DEG C, spiral shell
Bar rotating speed is 60r/min, is squeezed out, is granulated, and the particle that diameter and length are about 6mm is made, then adds above-mentioned parts by weight
Several starch interleaving agents is to get the pre-dispersed rubber master batch granule product ACT-70-2 of esters of acrylic acid rubber accelerator.
The pre-dispersed masterbatch particles ACT-70-2 of esters of acrylic acid rubber accelerator obtained above is subjected to in-vehicle air and vehicle
Inside gadget material organic volatile analyte detection (VOC), test result are：Ortho-aminotoluene ingredient is not detected.
In order to investigate the pre-dispersed masterbatch particles ACT-70-2 of esters of acrylic acid rubber accelerator obtained above to acrylate
The influence of rubber (ACM) vulcanizing system rheological property and physical property is used as using accelerating agent di-o-tolylguanidine (DOTG) and compareed,
Vulcanizing system design is carried out according to each group distribution ratio in table 4.
The vulcanizing system formula of 4 acrylic rubber of table
Fig. 2 and table 5 are respectively 1#Vulcanizing system and 2#The curing curve and rheological parameter of olefin(e) acid ester rubber under vulcanizing system.
From Fig. 2 and table 5 as can be seen that the accelerating agent masterbatch particles ACT-70-2 can not only substitute DOTG, and can also improve
The scorch safe and curing efficiency of acrylic rubber vulcanizing system.
The rheological parameter (vulcanization characteristics parameter) of acrylic rubber under 5 Elastomers with Different Curing Systems of table
| Performance parameter | 1# | 2# |
| Mooney viscosity, ML (1+4), 100 DEG C | 79 | 81 |
| TS1(s) | 47 | 45 |
| TS2(s) | 79 | 70 |
| TC10(s) | 41 | 39 |
| TC90(s) | 563 | 531 |
| ML(dN·m) | 2.04 | 2.13 |
| MH(dN·m) | 9.40 | 9.39 |
Table 6 is the physical property of acrylic rubber under Elastomers with Different Curing Systems.As can be seen from Table 6, using ACT-70-2
After substituting DOTG, the physical property of acrylic rubber can be kept, this shows that ACT-70-2 can substitute DOTG, and substitute
Compressive deformation makes moderate progress afterwards.
The physical property of acrylic rubber under 6 Elastomers with Different Curing Systems of table
| Performance parameter | 1# | 2# |
| Hardness | 63 | 65 |
| Elongation at break (%) | 243 | 224 |
| Tension (MPa) | 15.1 | 15.3 |
| Tearing strength (MPa) | 19.3 | 18.8 |
| Compressive deformation (%) | 8.7 | 10.4 |
Technical scheme of the present invention is described in detail in embodiment described above, it should be understood that the above is only
It for specific embodiments of the present invention, is not intended to restrict the invention, all any modifications made in the spirit of the present invention
With improve etc., should all be included in the protection scope of the present invention.
Claims (20)
1. a kind of pre-dispersed masterbatch particles of esters of acrylic acid rubber accelerator, it is characterized in that：Counted using parts by weight as 100 parts, by with
The component composition of lower parts by weight：
20~40 parts of acrylic polymer
10~25 parts of dialkyl dithiophosphate
20~40 parts of diamine compounds
20~40 parts of inorganic filler
1~10 part of operation oil.
2. the pre-dispersed masterbatch particles of esters of acrylic acid rubber accelerator as described in claim 1, it is characterized in that：The acrylic acid
Esters polymer includes acrylic rubber, ethylene-acrylate rubber, ethylene-methyl acrylate copolymer, ethylene-propylene
The mixture of one or more of acetoacetic ester copolymer.
3. the pre-dispersed masterbatch particles of esters of acrylic acid rubber accelerator as described in claim 1, it is characterized in that：The dialkyl group
Dithiophosphates is the dialkyl dithiophosphate that atomic number of alkyl carbon is 4~18.
4. the pre-dispersed masterbatch particles of esters of acrylic acid rubber accelerator as described in claim 1, it is characterized in that：The dialkyl group
Metal ion in dithiophosphates is the mixing of one or more of zinc, calcium, molybdenum, bismuth, magnesium metal ion.
5. the pre-dispersed masterbatch particles of esters of acrylic acid rubber accelerator as described in claim 1, it is characterized in that：The Diamines
Conjunction object is 2,5- diazabicyclos [2.2.1] heptane, 3,7- diazabicyclos [3.3.0] octane, 3,8- diazabicyclos
[3.2.1] octane, 1,4- diazabicyclos [3.2.2] nonane, 1,4- azabicyclos [4.3.0] nonane, 2,8- diazabicyclos
[4.3.0] nonane, 6,8- diazabicyclos [3.2.2] nonane, 1,4- diazabicyclos [4.3.1] decane, 1,8- diazas are double
The mixture of one or more of 11 carbon -7- alkene of ring [5.4.0].
6. the pre-dispersed masterbatch particles of esters of acrylic acid rubber accelerator as described in claim 1, it is characterized in that：It is described inorganic to fill out
Material includes the mixture of one or more of white carbon, calcium carbonate, talcum powder, clay, magnesium powder, carbon black, aluminium hydroxide.
7. the pre-dispersed masterbatch particles of esters of acrylic acid rubber accelerator as described in claim 1, it is characterized in that：The operation oil
It is the mixture of one or more of paraffinic, cycloalkane, arene.
8. the system of the pre-dispersed masterbatch particles of esters of acrylic acid rubber accelerator as described in any claim in claim 1 to 7
Preparation Method, it is characterized in that：Include the following steps：
(1) acrylic polymer carrier is added in by the parts by weight and is kneaded into mixer；
(2) inorganic filler, operation oil are added in into the mixer in step (1) and mixed respectively by the parts by weight
Refining；
(3) dialkyl dithiophosphate and diamine compounds are added in into step (2) respectively by the parts by weight
Mixer in be kneaded, be made sizing material；
(4) sizing material after being kneaded in step (3) is added in and is squeezed out, be granulated into single screw extrusion machine, pre-dispersed mother is made
Micelle.
9. the preparation method of the pre-dispersed masterbatch particles of esters of acrylic acid rubber accelerator as claimed in claim 8, it is characterized in that：Institute
It states in step (1), processing temperature is 30~80 DEG C, rotor speed is 20~80r/min.
10. the preparation method of the pre-dispersed masterbatch particles of esters of acrylic acid rubber accelerator as claimed in claim 8, it is characterized in that：
In the step (1), mixing time is 1~15min.
11. the preparation method of the pre-dispersed masterbatch particles of esters of acrylic acid rubber accelerator as claimed in claim 8, it is characterized in that：
In the step (1), mixing time is 5~8min.
12. the preparation method of the pre-dispersed masterbatch particles of esters of acrylic acid rubber accelerator as claimed in claim 8, it is characterized in that：
In the step (2), processing temperature is 30~80 DEG C, rotor speed is 20~80r/min.
13. the preparation method of the pre-dispersed masterbatch particles of esters of acrylic acid rubber accelerator as claimed in claim 8, it is characterized in that：
In the step (2), mixing time is 1~15min.
14. the preparation method of the pre-dispersed masterbatch particles of esters of acrylic acid rubber accelerator as claimed in claim 8, it is characterized in that：
In the step (2), mixing time is 5~8min.
15. the preparation method of the pre-dispersed masterbatch particles of esters of acrylic acid rubber accelerator as claimed in claim 8, it is characterized in that：
In the step (3), processing temperature is 50~80 DEG C, and rotor speed is 50~80r/min.
16. the preparation method of the pre-dispersed masterbatch particles of esters of acrylic acid rubber accelerator as claimed in claim 8, it is characterized in that：
In the step (3), mixing time is 1~30min.
17. the preparation method of the pre-dispersed masterbatch particles of esters of acrylic acid rubber accelerator as claimed in claim 8, it is characterized in that：
In the step (3), mixing time is 5~15min.
18. the preparation method of the pre-dispersed masterbatch particles of esters of acrylic acid rubber accelerator as claimed in claim 8, it is characterized in that：
In the step (4), the processing temperature of single screw extrusion machine is 50~80 DEG C, screw speed is 30~60r/min.
19. the preparation method of the pre-dispersed masterbatch particles of esters of acrylic acid rubber accelerator as claimed in claim 8, it is characterized in that：
In the step (4), a diameter of 5~20mm of pre-dispersed masterbatch particles, length is 5~25mm.
20. the preparation method of the pre-dispersed masterbatch particles of esters of acrylic acid rubber accelerator as claimed in claim 8, it is characterized in that：
In the step (4), after the obtained pre-dispersed masterbatch particles, a certain amount of interleaving agent is added.
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| CN105802100A (en) * | 2016-04-22 | 2016-07-27 | 宁波硫华聚合物有限公司 | Rubber accelerator bonding agent hexakis(methoxymethyl)melamine pre-dispersed rubber master batch particle and preparation method thereof |
| CN110591261B (en) * | 2019-09-21 | 2022-04-26 | 宁波艾克姆新材料股份有限公司 | Pre-dispersed masterbatch of vulcanization crosslinking activator of acrylate rubber and preparation method thereof |
| CN111154169B (en) * | 2019-11-11 | 2023-02-17 | 珠海科茂威新材料有限公司 | Rubber additive composition, preparation method thereof, rubber formulation and rubber product |
| CN111607180B (en) * | 2020-05-27 | 2022-03-08 | 中国科学院宁波材料技术与工程研究所 | Environment-friendly comprehensive accelerator pre-dispersed master batch and preparation method and application thereof |
| CN113337060B (en) * | 2021-05-20 | 2022-08-05 | 长园电子（东莞）有限公司 | Acrylate rubber material, preparation method thereof and heat-shrinkable sleeve |
| CN114316360A (en) * | 2022-01-07 | 2022-04-12 | 东莞市远鑫新材料有限公司 | Environment-friendly accelerant |
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| CN103857738A (en) * | 2011-10-11 | 2014-06-11 | 朗盛德国有限责任公司 | Vulcanisable compositions based on epoxy group-containing nitrile rubbers |
| CN103408851A (en) * | 2013-08-29 | 2013-11-27 | 宁波硫华聚合物有限公司 | Zinc dialkyl dithiophosphate pre-dispersion master colloidal particle and preparation method thereof |
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