CN105860168B - A kind of environmentally friendly low smell acrylonitrile rubber composite and preparation method - Google Patents
A kind of environmentally friendly low smell acrylonitrile rubber composite and preparation method Download PDFInfo
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- CN105860168B CN105860168B CN201610250391.1A CN201610250391A CN105860168B CN 105860168 B CN105860168 B CN 105860168B CN 201610250391 A CN201610250391 A CN 201610250391A CN 105860168 B CN105860168 B CN 105860168B
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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
- 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
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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
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- 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
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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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
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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
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/45—Heterocyclic compounds having sulfur in the ring
- C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
- C08K5/47—Thiazoles
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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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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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
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
Abstract
The present invention relates to a kind of low smell acrylonitrile rubber composite of environmental protection, include the component of following parts by weight：100 parts of nitrile rubber, 5~10 parts of zinc oxide, 1~3 part of stearic acid, 20~50 parts of fast extrude in carbon black, 20~50 parts of natural gas semi-reinforcing hydrocarbon black, 20~40 parts of strong prestige powder, 10~30 parts of plasticizer, 0.5~2 part of sulphur, comprehensive 2~10 parts of accelerator, 1~5 part of accelerator, 2~6 parts of age resistor, 0.5~2 part of eliminating smell agent.Plasticizer is plasticizer BXA R；Comprehensive accelerator is comprehensive accelerant B G187.The present invention employs fat hydrocarbon ester BXA R as plasticizer in nitrile rubber, with thiazoles, phosphordithiic acid salt and the mixture of foundation class accelerator are as comprehensive accelerator, and add eliminating smell agent SW120, the nitrile rubber product of preparation not only has excellent physical and mechanical properties, and product has no irritating odor, meet requirement of the main engine plants to environmentally friendly sebific duct.
Description
Technical field
The invention belongs to rubber materials, it is related to a kind of smell applied to rubber product than relatively low environmental protection formulae, specifically
It is a kind of low smell acrylonitrile rubber composite of environmental protection and preparation method.
Background technology
Nitrile rubber is famous with its excellent oil resistance, and nitrile rubber also has good wearability, airtight in addition
Property and electric conductivity, thus be used widely in rubber industry.The maximum consumption of nitrile rubber is production oil-resisting rubber hose product
And flame-retardant conveyor belt, consumption figure account for the 50% of nitrile rubber aggregate consumption.The development maked rapid progress with auto manufacturing
With reinforcement of the people to environmental consciousness, the bad smell that the rubber components of automobile accessories gives out also by rubber production person and
The concern of consumer, if people can make one to feel under the weather, can particularly cause consumer often in contact with this bad smell
Complaint.The rubber smell and volatile matter that domestic major automobile main frame maker is used automobile at present make strict regulations, i.e.,
Ask after rubber is deposited 2 hours at 80 DEG C that oder levels are less than equal to 3.5 grades, and according to standard (according to VDA270)
DIN75201B progress atomization tests obtain result requirement and are less than 5mg.
The experiment proved that smell main source is caused organic molecule in robber materialses or sulfidation：Ketone,
Amine, indoles, mercaptan, alkene etc..For the bad smell for overcoming rubber to give out, formula research staff devises many sides
Method, wherein main method is that eliminating smell agent or essence are added in formula, also has the baking processing of progress subsequent thermal unpleasant to eliminate
Smell and organic volatile, adding eliminating smell agent or essence can cause product to produce other peculiar smell, may be more unpleasant, rear process heat
Processing, although eliminating small molecule organic volatile, product produces and is charred taste, and waste of resource.Therefore, using the above method
Solve the low smell of rubber and reduce the measure of organic micromolecule compound volatilization, can not inherently solve rubber
Peculiar Smell, and product quality stability also cannot be guaranteed.
The content of the invention
To solve above-mentioned the deficiencies in the prior art, primary and foremost purpose of the invention is to provide a kind of environmental protection low smell butyronitrile rubber
Glue composition.
The purpose of the present invention is to be achieved through the following technical solutions：
A kind of environmentally friendly low smell acrylonitrile rubber composite, is made of the component of following parts by weight：Nitrile rubber 100
It is part, 5~10 parts of zinc oxide, 1~3 part of stearic acid, 20~50 parts of fast extrude in carbon black, 20~50 parts of natural gas semi-reinforcing hydrocarbon black, strong
It is 20~40 parts of prestige powder, 10~30 parts of plasticizer, 0.5~2 part of sulphur, comprehensive 2~10 parts of accelerator, 1~5 part of accelerator, anti-old
2~6 parts of agent, 0.5~2 part of eliminating smell agent.
Preferably, described environmentally friendly low smell acrylonitrile rubber composite is made of the component of following parts by weight：Fourth
100 parts of nitrile rubber, 5~6 parts of zinc oxide, 1~3 part of stearic acid, 25~50 parts of fast extrude in carbon black, natural gas semi-reinforcing hydrocarbon black 25~
50 parts, 20~40 parts of strong prestige powder, 15~25 parts of plasticizer, 0.5~1.5 part of sulphur, comprehensive 4~7 parts of accelerator, accelerator 4~5
Part, 1~3 part of age resistor, 1~2 part of eliminating smell agent.
Described strong prestige powder is strong prestige powder KTC.
Described plasticizer is plasticizer BXA-R.
Described synthesis accelerator is comprehensive accelerant B G187, and comprehensive accelerant B G187 is thiazoles, phosphordithiic acid
The mixing synthesis accelerator of salt and foundation class accelerator.Described accelerator is captax g (MAA)2, captax g (MAA)2
For methyl methacrylate magnesium.
Described age resistor is anti-aging agent RD and antioxidant 4010NA according to weight ratio 1：1 blended antioxidant.Age resistor
RD is 2,2,4 trimethyl 1,2 dihydroquinoline polymer；Antioxidant 4010NA is N- isopropyls-N '-diphenyl-para-phenylene diamine.
Described eliminating smell agent is eliminating smell agent SW120, and eliminating smell agent SW120 is salt compounds.
The preparation method of the low smell acrylonitrile rubber composite of environmental protection of the present invention, including：
(1), banbury water flowing cools down, and control banbury works room temperature no more than 50 DEG C, and nitrile rubber mixing 1~
1.5min, sequentially add zinc oxide, stearic acid, age resistor and be kneaded 2~5min；It is subsequently added into fast extrude in carbon black, natural gas half
Hard carbon black, strong prestige powder, plasticizer are kneaded 3~5min；Finally, sulphur is added, comprehensive accelerator, accelerator and eliminating smell agent are kneaded
2~3min；Afterwards, cooling water of banbury mixer is closed, continues banburying, when banbury temperature rises to 110 DEG C, dumping, moves to opening
Thin pass-out piece is carried out on formula rubber mixing machine；
(2), mixture made from step (1) is vulcanized in vulcanizing press, 160 DEG C of curing temperature, during vulcanization
Between 15min, obtain acrylonitrile rubber composite.Under the conditions of vulcanization, the correlated performance of sulfide film reaches Shao A of hardness 70 ± 5,
Tensile strength is more than 10MPa.
Compared with prior art, beneficial effects of the present invention：
Fat hydrocarbon ester BXA-R is employed in acrylonitrile rubber composite of the present invention as plasticizer, it is thio with thiazoles, two
Phosphoric acid salt and the mixture of foundation class accelerator add eliminating smell agent SW120 as comprehensive accelerator, the nitrile rubber of preparation
Product not only has excellent physical and mechanical properties, and product has no irritating odor, and middle grade is tested at 3.5 grades in smell
Hereinafter, atomization test result is less than 0.5mg, meets requirement of the main engine plants to environmentally friendly sebific duct.
Embodiment
Technical scheme is further illustrated with reference to specific embodiment.
A kind of environmentally friendly low smell acrylonitrile rubber composite, its component and parts by weight are as shown in table 1, according to following preparation side
It is prepared by method：
(1), banbury water flowing cools down, and control banbury work room temperature is less than 50 DEG C, and 30 revs/min of rotating speed is right first
Nitrile rubber carries out 1~1.5min of mixing；Sequentially add zinc oxide, stearic acid, age resistor and carry out 2~5min of mixing；Again plus
Enter fast extrude in carbon black, natural gas semi-reinforcing hydrocarbon black, strong prestige powder, plasticizer and carry out 3~5min of mixing；Finally, add sulphur, promote
Agent, and/or comprehensive accelerator, and/or eliminating smell agent, carry out 2~3min of mixing；Afterwards, cooling water of banbury mixer is closed, is continued close
Refining, dumping when banbury temperature rises to 110 DEG C, moves on opening rubber mixing machine and carries out thin pass-out piece；
(2) mixture made from step (1) is vulcanized in vulcanizing press, 160 DEG C of curing temperature, cure time
15min, obtain acrylonitrile rubber composite.
The component and weight fraction of the embodiment 1-4 of table 1 and comparative example 1-2 acrylonitrile rubber composite
| Ingredient names | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 |
| Nitrile rubber | 100 | 100 | 100 | 100 | 100 | 100 |
| Zinc oxide | 5 | 5 | 5 | 5 | 5 | 5 |
| Stearic acid | 1 | 1 | 1 | 1 | 1 | 1 |
| Fast extrude in carbon black | 25 | 45 | 45 | 50 | 45 | 45 |
| Natural gas semi-reinforcing hydrocarbon black | 50 | 45 | 45 | 25 | 45 | 45 |
| Strong prestige powder KTC(1) | 40 | 20 | 25 | 30 | 20 | 20 |
| Plasticizer BXA-R(2) | 15 | 15 | 20 | 25 | 15 | 15 |
| Sulphur | 0.5 | 0.8 | 1.2 | 1.5 | 0.8 | 0.8 |
| Comprehensive accelerant B G187(3) | 7 | 6 | 5 | 4 | - | 6 |
| Captax g (MAA)2 (4) | 5 | 5 | 4 | 4 | 5 | 5 |
| Accelerant CZ | - | - | - | - | 1 | - |
| Vulcanization accelerator TMTD | - | - | - | - | 1 | - |
| Diphenylguanidine TDM | - | - | - | - | 1 | - |
| Anti-aging agent RD | 1 | 1 | 1 | 1 | 1 | 1 |
| Antioxidant 4010NA | 1 | 1 | 1 | 1 | 1 | 1 |
| Eliminating smell agent SW120(5) | 1 | 1.5 | 1.5 | 2 | 1.5 | - |
Note：(1) the strong prestige powder KTC of, it is that a kind of double layer surface is modified the silicate supporting material formed, has scattered, micro-
The features such as structure remains intact is seen, extruded velocity and surface flatness can be improved, improves insulating articles and osmotic-pressure-tolerant.
(2) plasticizer BXA-R, two sweet ester of main component adipic acid dibutyl, can not only effectively improve the processing of sizing material
Performance, and have good compatibility with nitrile rubber, volatility is low, and environmental-protecting performance is good.
(3) integrates the mixture that accelerant B G187 is thiazoles, phosphordithiic acid salt and foundation class accelerator, in sulphur
To change in reaction, be not easy to generate secondary amine, curingprocess rate is fast, has good heat-proof aging and compression resistant permanent deformation performance, and
And the smell of vulcanizate is very low.
(4) eliminating smell agents SW120 is salt compounds, using salt compounds as eliminating smell agent, such as ferrous ion and
Ascorbic acid suppresses to aoxidize together, is allowed to become free from extraneous odour material with smell substance reactions such as ammonia, mercaptan；Ferric iron derives
Displacement reaction occurs for thing, the ligand of metal complex and mercaptan or sulphur, and smell substance is converted into free from extraneous odour material, improves life
Produce the Environmental Protection Level of environment and product.
(5) captaxs g (MAA)2It is methyl methacrylate magnesium, is a kind of salt unsaturated carboxylic acid, can be with nitrile rubber point
Son occur graft reaction, formed inierpeneirating network structure, be advantageous to transmit and dispersive stress, add network be effectively crosslinked it is close
Degree, plays good humidification.
Nitrile rubber product made of embodiment 1-4, comparative example 1-2 according to《GB/T531.1-2008》、《GB/T528-
2009》Examination criteria carries out detection experiment, as a result as shown in table 2.
The embodiment 1-4 of table 2 and comparative example 1-2 acrylonitrile rubber composites performance parameter
Interpretation of result：It can show that the technical indicator of acrylonitrile rubber composite of the present invention complies fully with skill from the data of table 2
Art index request, middle grade is tested below 3.5 grades in smell, atomization test result is less than 0.5mg, is prepared by the formula
Sebific duct has not only reached the performance requirement needed for product, and product odour is low, meets that each main engine plants carry to rubber at present
The environmental requirement gone out.
Claims (4)
1. a kind of environmentally friendly low smell acrylonitrile rubber composite, it is characterised in that it is made of the component of following parts by weight：
100 parts of nitrile rubber, 5~10 parts of zinc oxide, 1~3 part of stearic acid, 20~50 parts of fast extrude in carbon black, natural gas semi-reinforcing hydrocarbon black
20~50 parts, 20~40 parts of strong prestige powder, 10~30 parts of plasticizer, 0.5~2 part of sulphur, comprehensive 2~10 parts of accelerator, accelerator 1
~5 parts, 2~6 parts of age resistor, 0.5~2 part of eliminating smell agent；Wherein, described strong prestige powder is strong prestige powder KTC, and described plasticizer is
Plasticizer BXA-R, described synthesis accelerator are comprehensive accelerant B G187, and described accelerator is captax g (MAA)2, institute
The eliminating smell agent stated is eliminating smell agent SW120.
2. the low smell acrylonitrile rubber composite of environmental protection according to claim 1, it is characterised in that described environmentally friendly low smell
Acrylonitrile rubber composite is made of the component of following parts by weight：100 parts of nitrile rubber, 5~6 parts of zinc oxide, stearic acid 1
~3 parts, 25~50 parts of fast extrude in carbon black, 25~50 parts of natural gas semi-reinforcing hydrocarbon black, 20~40 parts of strong prestige powder, plasticizer 15~25
Part, 0.5~1.5 part of sulphur, comprehensive 4~7 parts of accelerator, 4~5 parts of accelerator, 1~3 part of age resistor, 1~2 part of eliminating smell agent.
3. the low smell acrylonitrile rubber composite of environmental protection according to claim 1 or 2, it is characterised in that described age resistor is
Anti-aging agent RD and antioxidant 4010NA are according to weight ratio 1：1 blended antioxidant.
4. the preparation method of the environmentally friendly low smell acrylonitrile rubber composite described in claim 1, it is characterised in that including：
(1), banbury water flowing cools down, and control banbury work room temperature is no more than 50 DEG C, and nitrile rubber is kneaded 1~1.5min,
Sequentially add zinc oxide, stearic acid, age resistor and be kneaded 2~5min；It is subsequently added into fast extrude in carbon black, the reinforcement charcoal of natural gas half
Black, strong prestige powder, plasticizer are kneaded 3~5min；Finally, add sulphur, comprehensive accelerator, accelerator and eliminating smell agent be kneaded 2~
3min；Afterwards, cooling water of banbury mixer is closed, continues banburying, when banbury temperature rises to 110 DEG C, dumping, moves to open refining
Thin pass-out piece is carried out on glue machine；
(2), mixture made from step (1) is vulcanized in vulcanizing press, 160 DEG C of curing temperature, cure time
15min, obtain acrylonitrile rubber composite.
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| CN109354782A (en) * | 2018-11-21 | 2019-02-19 | 四川福翔科技有限公司 | Applied to composition, preparation method and the rubber tube for preparing rubber tube |
| CN110256986A (en) * | 2019-06-03 | 2019-09-20 | 贵州大自然科技股份有限公司 | A kind of plant-fiber mattress is combined with low smell adhesive promoter and application method |
| CN110577677A (en) * | 2019-10-17 | 2019-12-17 | 宁波市北仑优联特橡塑制品有限公司 | Odorless environment-friendly nitrile rubber and preparation method thereof |
| CN113024910A (en) * | 2021-03-05 | 2021-06-25 | 安徽中鼎密封件股份有限公司 | Nitrile rubber product material with low polycyclic aromatic hydrocarbon content |
| CN114249929B (en) * | 2021-12-17 | 2023-11-28 | 南京利德东方橡塑科技有限公司 | Sheath tube of underwater pluggable optical fiber connector and manufacturing method thereof |
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| CN103819733B (en) * | 2014-02-21 | 2016-03-23 | 宁波硫华聚合物有限公司 | The pre-dispersed masterbatch particles of weather strip for automobile Environmental-protection comprehensive promotor and preparation thereof |
| CN104277337A (en) * | 2014-09-28 | 2015-01-14 | 湖北诺克橡塑密封科技有限公司 | Automobile sealing strip as well as smell and VOC (volatile organic compound) control method |
| CN105001524A (en) * | 2015-07-14 | 2015-10-28 | 宁国市正道橡塑零部件有限公司 | Rubber material used for automotive wire harness and preparation method thereof |
| CN105504549A (en) * | 2016-01-22 | 2016-04-20 | 太仓冠联高分子材料有限公司 | Low-VOC and smell-free environmental-protection automobile sealing strip rubber and preparation method thereof |
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