CN107488120B - A kind of multi-quaternary ammonium salt rubber accelerator preparation method and the rubber containing the promotor - Google Patents
A kind of multi-quaternary ammonium salt rubber accelerator preparation method and the rubber containing the promotor Download PDFInfo
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- CN107488120B CN107488120B CN201710639170.8A CN201710639170A CN107488120B CN 107488120 B CN107488120 B CN 107488120B CN 201710639170 A CN201710639170 A CN 201710639170A CN 107488120 B CN107488120 B CN 107488120B
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- quaternary ammonium
- ammonium salt
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/04—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reaction of ammonia or amines with olefin oxides or halohydrins
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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
- C08L7/00—Compositions of natural rubber
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Sealing Material Composition (AREA)
Abstract
The invention discloses a kind of multi-quaternary ammonium salt rubber accelerator preparation method and its contain the rubber compounding of the promotor.The preparation method of promotor is first to be dissolved in ethylenediamine and epoxychloropropane in alcohol solvent with the molar ratio of 1:5 intermediate is made；Hereafter, intermediate and long chain tertiary amine C18H37N (CH3) 2 are dissolved in ethyl alcohol and deionized water solvent with the molar ratio of 1:5 is made multi-quaternary ammonium salt rubber accelerator again.Use the promotor rubber compounding change for；99.7% zinc oxide is reduced to 0.5 part；Newly-increased 0.5 part of quaternary ammonium salt accelerator；Other same conventional formulations.The present invention is by changing monomeric species, structural unit connection type, sequence distribution and monomer composition, it is prepared for the polymeric quaternary ammonium salt molecule with specified structure, establish products molecule structure, have developed a kind of novel high polymer quaternary ammonium salt rubber accelerator, forming complex compound with Sulfur using it activates Sulfur, to improve sealing material physical property, solve the problems, such as that traditional promotor pyrolytic nitrosamine is carcinogenic.
Description
Technical field
The present invention relates to technical field of rubber preparation, in particular to the preparation sides of a kind of rubber accelerator and the promotor
Method.
Background technique
Rubber accelerator can promote rubber product physical properties, be widely used in field of rubber preparation at present.
Although rubber accelerator can be obviously improved rubber product physical properties, external lot of experiments is proved, contains secondary amine
The promotor of base can generate carcinogen nitrosamine in sulfidation, and to human health, there are potential threats.This is involved in
Quite a lot of now widely used promotor kind, accelerant NOBS, DIBS, DCBS, OTOS of such as sulfenamide；Qiu Lan
TMTM, TMTD, TETD of nurse class；PZ, EZ and sulphur-donor DTDM, TTDM of dithiocarbamates etc..With
The environmentally safe pay attention to day by day with environmental health of the common people, a kind of environmental-friendly and excellent effect promotor of exploitation, has aobvious
The realistic meaning of work.
In addition, zinc oxide (ZnO) is also widely used in rubber seal products as activating agent for rubber, although it is generally acknowledged that
Zinc is the smallest heavy metal of toxicity, but still is put into and suspects in environmentally harmful Priority Substances List.Studies have shown that some water
Biological species are to the zinc of very low amount with regard to very sensitive, and therefore, soluble zinc compound is divided into toxic to the ecology of aquatic organisms
Substance.ZnO is also possible to be classified as this kind, thus may will limit oxygen-containingization zinc product in rubber product industry from now on
Production and use.It is powdery since ZnO is easily lost especially in sealing article, diffusion is very fast, can generate immediately to algae
Local toxicity, this will bring huge environment hidden danger to natural water.
In general, rubber accelerator next stage development trend will be needed on the basis of guaranteeing preferable facilitation effect
Ask safety and the feature of environmental protection, solve the problems, such as it is high temperature vulcanized under the conditions of decompose the nitrosamine carcinogenicity of generation；Meanwhile passing through novel rubber
The research and development of promoter for rubber use, and reduce dosage of the ZnO in rubber compounding and especially drop to avoid environment and water pollution
The low potential threat in sealing article, is of great significance.
Summary of the invention
It is an object of the invention to provide the quaternary ammonium salt promotors of a kind of safety and the feature of environmental protection.
The purpose of the present invention is achieved through the following technical solutions:
A kind of multi-quaternary ammonium salt rubber accelerator preparation method, the processing step of the preparation method is:
(1) ethylenediamine and epoxychloropropane are dissolved in alcohol solvent with the molar ratio of 1:5, are 70 DEG C in reaction temperature,
Intermediate, reaction equation is made under the process conditions that reaction time is 4h are as follows:
At the process conditions, the yield of intermediate is 83.5%；
(2) intermediate made from step (1) and C18H37N (CH3) 2, are dissolved in ethyl alcohol and deionization with the molar ratio of 1:5
In aqueous solvent, it is 80 DEG C in reaction temperature, multi-quaternary ammonium salt rubber accelerator, reaction is made under the process conditions that the reaction time is 1h
Equation are as follows:
Under the reaction conditions, the yield of multi-quaternary ammonium salt rubber accelerator is 67.1%.
The promotor is as one of rubber components, rubber quality proportion are as follows: and 40 parts of natural gum NR, precipitated calcium carbonate 10
Part；6 parts of machine oil, 12 parts of N330 carbon black；99.7% 0.5~0.8 part of zinc oxide；0.4~0.6 part of quaternary ammonium salt accelerator；Stearic acid
0.6 part of SA；0.1 part of anti-aging agent RD；0.4 part of rubber antioxidant 4010NA；0.24 part of paraffin；0.10 part of captax；Promote
0.40 part of agent DTDM；0.60 part of accelerant NOBS；0.10 part of Vulcanization accelerator TMTD；0.10 part of sulphur S.
Further, as a preference, the rubber quality matches are as follows: 40 parts of natural gum NR, 10 parts of precipitated calcium carbonate；
6 parts of machine oil, 12 parts of N330 carbon black；99.7% 0.5 part of zinc oxide；0.5 part of quaternary ammonium salt accelerator；0.6 part of stearic acid SA；It is anti-old
0.1 part of agent RD；0.4 part of rubber antioxidant 4010NA；0.24 part of paraffin；0.10 part of captax；Diphenylguanidine TDM 0.40
Part；0.60 part of accelerant NOBS；0.10 part of Vulcanization accelerator TMTD；0.10 part of sulphur S.
Compared with prior art, the beneficial effects of the present invention are:
The present invention is prepared for having by changing monomeric species, structural unit connection type, sequence distribution and monomer composition
The polymeric quaternary ammonium salt molecule of specified structure, establishes products molecule structure, has developed a kind of novel high polymer quaternary ammonium salt rubber
Promoter for rubber, forming complex compound with Sulfur using it activates Sulfur, to improve sealing material physical property, solves tradition and promotees
Into the carcinogenic problem of agent pyrolytic nitrosamine.In addition zinc oxide can be used no or little in formula, also solves oxide powder and zinc pair
Environment and water pollution can be applied in the higher product of environmental requirement convenient for product sealing ring.It follows that institute of the present invention
Being related to high molecular quaternary is one kind using carbon, hydrogen, oxygen as main chain, and quaternary ammonium group is located at the promotor of side chain.Such polyacids quaternary ammonium salt
The existing main chain based on oleophylic, also there is hydrophilic side chain, therefore has good activation.
Specific embodiment
Following non-limiting examples are for illustrating this explanation.
As unit of mass fraction, rubber original formulation (does not contain quaternary ammonium salt accelerator): natural gum NR 40kg, lightweight carbon
Sour calcium 10kg；Machine oil 6kg, N330 carbon black 12kg；99.7% zinc oxide 1.5kg；Stearic acid SA 0.6kg；Anti-aging agent RD
0.1kg；Rubber antioxidant 4010NA 0.4kg；Paraffin 0.24kg；Captax 0.10kg；Diphenylguanidine TDM 0.40kg；Promote
Agent NOBS 0.60kg；Vulcanization accelerator TMTD 0.10kg；Sulphur S 0.10kg.
Using rubber made from above-mentioned formula, the physical property measured is as follows:
Hardness (HS) 54-56
Intensity >=Mpa 22
Elongation >=%480%
Buckling (70 × for 24 hours)≤20%
Embodiment one
Using the rubber compounding for including quaternary ammonium salt accelerator are as follows: natural gum NR 40kg, precipitated calcium carbonate 10kg；Machine oil
6kg, N330 carbon black 12kg；99.7% 0.5~0.8kg of zinc oxide；Quaternary ammonium salt accelerator 0.4kg；Stearic acid SA 0.6kg；It is anti-old
Agent RD 0.1kg；Rubber antioxidant 4010NA 0.4kg；Paraffin 0.24kg；Captax 0.10kg；Diphenylguanidine TDM
0.40kg；Accelerant NOBS 0.60kg；Vulcanization accelerator TMTD 0.10kg；Sulphur S 0.10kg.
Using rubber made from above-mentioned formula, the physical property measured is as follows:
Hardness (HS) 54-56
Intensity >=Mpa 23
Elongation >=% 500%
Buckling (70 × for 24 hours)≤20%
Embodiment two
Using the rubber compounding for including quaternary ammonium salt accelerator are as follows: natural gum NR 40kg, precipitated calcium carbonate 10kg；Machine oil
6kg, N330 carbon black 12kg；99.7% 0.5~0.8kg of zinc oxide；Quaternary ammonium salt accelerator 0.5kg；Stearic acid SA 0.6kg；It is anti-old
Agent RD 0.1kg；Rubber antioxidant 4010NA 0.4kg；Paraffin 0.24kg；Captax 0.10kg；Diphenylguanidine TDM0.40kg；
Accelerant NOBS 0.60kg；Vulcanization accelerator TMTD 0.10kg；Sulphur S 0.10kg.
Using rubber made from above-mentioned formula, the physical property measured is as follows:
Hardness (HS) 54-56
Intensity >=Mpa 23.5
Elongation >=% 510%
Buckling (70 × for 24 hours)≤20%
Embodiment three
Using the rubber compounding for including quaternary ammonium salt accelerator are as follows: natural gum NR 40kg, precipitated calcium carbonate 10kg；Machine oil
6kg, N330 carbon black 12kg；99.7% 0.5~0.8kg of zinc oxide；Quaternary ammonium salt accelerator 0.6kg；Stearic acid SA 0.6kg；It is anti-old
Agent RD 0.1kg；Rubber antioxidant 4010NA 0.4kg；Paraffin 0.24kg；Captax 0.10kg；Diphenylguanidine TDM
0.40kg；Accelerant NOBS 0.60kg；Vulcanization accelerator TMTD 0.10kg；Sulphur S 0.10kg.
Using rubber made from above-mentioned formula, the physical property measured is as follows:
Hardness (HS) 54-56
Intensity >=Mpa 23.2
Elongation >=% 503%
Buckling (70 × for 24 hours)≤20%
As can be seen from the above embodiments, by increasing quaternary ammonium salt accelerator newly in this formula, it is possible to reduce the dosage of zinc oxide, together
Sample has better meet the mechanical property requirements of rubber product.Solves the problems, such as oxide powder and zinc to environment and water pollution, just
It can be applied in the higher product of environmental requirement in product sealing ring.
Claims (3)
1. a kind of multi-quaternary ammonium salt rubber accelerator preparation method, which is characterized in that the processing step of the preparation method is:
(1), ethylenediamine and epoxychloropropane are dissolved in alcohol solvent with the molar ratio of 1:5, are 70oC, reaction in reaction temperature
Intermediate, the molecular structure of the intermediate is made under the process conditions that time is 4h are as follows:
(2) intermediate made from step (1) is dissolved in ethyl alcohol with C18H37N (CH3) 2 with the molar ratio of 1:5 and deionization is water-soluble
In agent, it is 80oC in reaction temperature, multi-quaternary ammonium salt rubber accelerator is made under the process conditions that the reaction time is 1h, it is described more
The molecular structure of quaternary ammonium salt rubber accelerator are as follows:
。
2. the rubber comprising promotor described in claim 1, which is characterized in that rubber quality proportion are as follows: natural gum NR 40
Part, 10 parts of precipitated calcium carbonate；6 parts of machine oil, 12 parts of N330 carbon black；99.7% 0.5 ~ 0.8 part of zinc oxide；Quaternary ammonium salt accelerator
0.4 ~ 0.6 part；0.6 part of stearic acid SA；0.1 part of anti-aging agent RD；0.4 part of rubber antioxidant 4010NA；0.24 part of paraffin；
0.10 part of captax；0.40 part of diphenylguanidine TDM；0.60 part of accelerant NOBS；0.10 part of Vulcanization accelerator TMTD；Sulphur S
0.10 part.
3. rubber according to claim 2, which is characterized in that rubber quality proportion are as follows: 40 parts of natural gum NR, lightweight
10 parts of calcium carbonate；6 parts of machine oil, 12 parts of N330 carbon black；99.7% 0.5 part of zinc oxide；0.5 part of quaternary ammonium salt accelerator；It is stearic
0.6 part of sour SA；0.1 part of anti-aging agent RD；0.4 part of rubber antioxidant 4010NA；0.24 part of paraffin；Captax 0.10
Part；0.40 part of diphenylguanidine TDM；0.60 part of accelerant NOBS；0.10 part of Vulcanization accelerator TMTD；0.10 part of sulphur S.
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| CN201710639170.8A CN107488120B (en) | 2017-07-31 | 2017-07-31 | A kind of multi-quaternary ammonium salt rubber accelerator preparation method and the rubber containing the promotor |
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Effective date of registration: 20211202 Address after: 629300 xijiagou Industrial Development Zone, Daying County, Suining City, Sichuan Province Patentee after: SICHUAN JUST RUBBER Co.,Ltd. Address before: 643000 group 7, huangjuewan, Lianggaoshan street, Da'an District, Zigong City, Sichuan Province Patentee before: ZIGONG JUST SEALING PRODUCTS Co.,Ltd. |