CN105860174B - A kind of XNBR vulcanization of rubber glue with self-healing properties and preparation method thereof - Google Patents
A kind of XNBR vulcanization of rubber glue with self-healing properties and preparation method thereof Download PDFInfo
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- CN105860174B CN105860174B CN201610244284.8A CN201610244284A CN105860174B CN 105860174 B CN105860174 B CN 105860174B CN 201610244284 A CN201610244284 A CN 201610244284A CN 105860174 B CN105860174 B CN 105860174B
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- xnbr
- pva
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- healing properties
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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
- C08L13/00—Compositions of rubbers containing carboxyl groups
- C08L13/02—Latex
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention provides a kind of XNBR vulcanizates with self-healing properties, including following components：The mass parts of XNBR 100, the mass parts of PVA 20~40, the mass parts of aminated compounds 0.3~0.6, the mass parts of vulcanizing agent 0.8~2.5, the mass parts of accelerator 0.1~0.5.Present invention also offers a kind of preparation method of the XNBR vulcanization of rubber glue with self-healing properties, using emulsion blending, after by PVA solution and the blending of XNBR latex, aminated compounds, vulcanizing agent and accelerator are added, the XNBR vulcanization of rubber glue containing PVA of the invention is prepared by vulcanizing processing.The present invention passes through latex blending method, improve degrees of scatter of the PVA in XNBR, the fracture using the hydrogen bond formed between PVA and aminated compounds and bonding process again, improve the mechanical strength and self-reparing capability of XNBR simultaneously, prepare the XNBR vulcanizates with superperformance.
Description
Technical field
Vulcanization of rubber glue and its preparation the present invention relates to a kind of XNBR (XNBR) with self-healing properties
Method, belongs to rubber polymer technical field of composite preparation.
Background technology
Rubber is the important foundation material in industrial production, is important strategic materials.In the use process of rubber
In, rubber is acted on down by alternate stress, produces micro-crack, and then Crack Extension, forms destruction, is ultimately resulted in material and is broken
Split, lose use value.Therefore research elastomeric material self-reparing capability in use, is always the research of rubber materials
Focus.
Selfreparing research currently for rubber is concentrated mainly on two aspects, and one is that renovation agent is introduced in rubber, is led to
Polymerization or bonding of the renovation agent in cracks are crossed, selfreparing (the Adv Funct Mater, 2007,17 of elastomeric material is realized:
2399-2404,Macromole Mater Eng,2012,297:411-419), but in the method, the renovation agent of introducing is easy
Stress concentration point is formed in elastomeric material, the mechanical property of rubber is seriously reduced；Two is, by MOLECULE DESIGN, to synthesize main chain
The upper novel elastomer with a large amount of hydrogen bonds, by being bonded again for cracks hydrogen bond, reach crackle selfreparing (Nature,
2008,451:977-980,J PolymSci,2013,31:251-262,J Appl Polym Sci,2013,129:2435-
2442), however, very low by the constructed mechanics of elastic bodies intensity of hydrogen bond, do not have practical value.Therefore rubber material is being ensured
On the mechanical strength of material, the self-reparing capability of rubber is improved, be the previous urgent problem of mesh.
The content of the invention
The technical problems to be solved by the invention are the defects for overcoming prior art, there is provided one kind have strong mechanical performance and
XNBR vulcanization of rubber glue of good selfreparing effect and preparation method thereof.
In order to solve the above technical problems, the present invention provides a kind of XNBR vulcanization of rubber glue with self-healing properties, it is special
Levy and be, including following components：The mass parts of XNBR 100, the mass parts of PVA 20~40, the mass parts of aminated compounds 0.3~0.6,
The mass parts of vulcanizing agent 0.8~2.5, the mass parts of accelerator 0.1~0.5.
Further, the matter average molecular weight of the PVA is 95000~100000, and alcoholysis degree is 60%.
Further, the vulcanizing agent is sulphur, and the accelerator is zinc dithiocarbamate, diethyl-dithio ammonia
One or two in base zinc formate.
Further, the aminated compounds is the one kind in 2,4,6- Triaminopyrimidines, 2,4,5,6- tetraminopyrimidines
Or two kinds.
Present invention also offers a kind of preparation method of the XNBR vulcanization of rubber glue with self-healing properties, its feature exists
In comprising the following steps：
Step one：PVA is weighed, is added in 95 DEG C of deionized waters, stirring and dissolving, filtered, cooling obtains PVA solution；
Step 2：The PVA solution that step one is obtained is blended with XNBR latex, ultrasound, adds aminated compounds, sulphur
Agent, accelerator, stirring, obtain PVA/XNBR mixed solutions, are poured into mould, dry obtain PVA/XNBR glue at room temperature
Film；
Step 3：The PVA/XNBR glued membranes that step 2 is obtained sulfidization molding in an oven, obtains with self-healing properties
XNBR vulcanization of rubber glue.
Further, ultrasonic time is 0.5~1 hour in the step 2, and ultrasonic power is 125~250W, and temperature is
20~60 DEG C.
Further, the aminated compounds, vulcanizing agent, the addition sequence of accelerator are vulcanizing agent, aminated compounds, rush
Enter agent, the interval time for often adding a class material is 0.5h.
Further, in the step 3, curing temperature is 60 DEG C, and the time is 20min.
The beneficial effect that the present invention is reached：
(1) by emulsion dispersion, enable PVA and XNBR homogeneous blends, increase degrees of scatter of the PVA in XNBR,
The purpose for improving XNBR mechanical strengths is reached, in the present invention, after PVA is added, tensile strength and the tearing strength ratio of vulcanizate
Vulcanizate highest without PVA can increase by 330% and 150% respectively.
(2) hydrogen bond crosslinks network is formd in XNBR due to PVA, the fracture by hydrogen bond be bonded again, effectively carry
The self-reparing capability of XNBR vulcanizates high, in the present invention, the self-reparing capability of XNBR vulcanizates is up to 70%.
Brief description of the drawings
Fig. 1 is the flow chart of the preparation method of the XNBR vulcanization of rubber glue with self-healing properties of the invention.
Specific embodiment
The invention will be further described below in conjunction with the accompanying drawings.Following examples are only used for clearly illustrating the present invention
Technical scheme, and can not be limited the scope of the invention with this.
The present invention utilizes emulsion dispersion, improves degrees of scatter of the PVA in XNBR, improves the mechanical strength of XNBR；Profit
Fracture and bonding process again with the hydrogen bond formed between PVA, prepare the XNBR vulcanizates with good self-reparing capability.
In the method can be widely used in all kinds of specific rubber products, it is high to be particularly well-suited to mechanical property requirements, service life
Rubber long.
The invention provides a kind of XNBR vulcanization of rubber glue with strong mechanical performance, including following components：XNBR 100
Mass parts, matter average molecular weight is the mass parts of PVAC polyvinylalcohol 20~40 that 95000~100000, alcoholysis degree is 60%, amine
The mass parts of compound 0.3~0.6, the mass parts of vulcanizing agent 0.8~2.5, the mass parts of accelerator 0.1~0.5.
The vulcanizing agent is sulphur, and the accelerator is zinc dithiocarbamate, zinc diethyl dithiocarbamate
In one or two.
The aminated compounds be 2,4,6- Triaminopyrimidines, 2,4,5,6- tetraminopyrimidines in one or two.
Present invention also offers a kind of preparation method of the XNBR vulcanization of rubber glue with strong mechanical performance, including following step
Suddenly：
Step one：PVA is weighed, is added in 95 DEG C of deionized waters, stirring and dissolving, filtered, cooling obtains PVA solution；
Step 2：The PVA solution that step one is obtained is blended with XNBR latex, ultrasound, adds aminated compounds, sulphur
Agent, accelerator, stirring, obtain PVA/XNBR mixed solutions, are poured into mould, dry obtain PVA/XNBR glue at room temperature
Film；
Step 3：The PVA/XNBR glued membranes that step 2 is obtained sulfidization molding in an oven, obtains with strong mechanical performance
XNBR vulcanization of rubber glue.
The XNBR vulcanizations of rubber glue of obtained strong mechanical performance is carried out into following performance test：
(1) tensile property：
Thought carefully in Shenzhen according to GB/T528-2009 standards and tested on CMT4254 electronic universal puller systems, stretching speed
It is 500mm/min to spend.Record determining to stretch 100% modulus (M100), 300% modulus (M300), tensile strength being stretched surely, is broken for vulcanizate
Split elongation.Sample with bigger tensile strength is better.
(2) tear resistance：
Tear resistance test is thought carefully in Shenzhen according to GB/T529-2008 standards and carried out on CMT4254 electronic universal puller systems
Test, speed is 500mm/min, records the tearing strength of vulcanizate.Sample with bigger tearing strength is better.
(3) self-healing properties：
Sample after tension failure is brought into close contact in incision position, is placed on 40 DEG C of flat boards after 6h, retest vulcanization
The tensile property of glue, calculates the initial drawing of the tensile strength/vulcanizate of the self-reparing capability R=selfreparing after cure glue of vulcanizate
Stretch intensity × 100%.Sample with bigger R values is better.
(4) bounce impact elasticity：
Bounce impact elasticity is tested according on GB/T1681-1991 standard impulse resiliometers, records rebound value.With more
The vulcanizate of big rebound value is better.
Below by embodiment and comparative example, the invention will be further described.
Embodiment 1
20gPVA is weighed, is added in 180g, 95 DEG C of deionized water, stirring and dissolving is filtered while hot, stand cooling, obtained
To PVA solution；215gXNBR latex (XNBR dry glues amount is 100g) is weighed, is blended with above-mentioned PVA solution, ultrasonic 0.5h, work(
Rate is 250W, and 20 DEG C of temperature adds 2,4,5,6- tetraminopyrimidine 0.6g, stirs 0.5 hour, adds sulphur 0.8g, stirring 0.5
Hour, zinc dithiocarbamate 0.5g is added, stirring obtains PVA/XNBR mixed solutions, is poured into mould, in room temperature
Under dry and obtain XNBR glued membranes；The glued membrane that will be obtained heats 20min in 60 DEG C of baking ovens, and sulfidization molding is obtained with selfreparing
The XNBR vulcanization of rubber glue of performance.Related procedure is as shown in Figure 1.Vulcanizate detailed performance such as table 1.
Embodiment 2
The method that embodiment 1 is repeated by each component content specified, but 30gPVA is used in formula.Vulcanizate is details
Can be such as table 1.
Embodiment 3
The method that embodiment 1 is repeated by each component content specified, but 40gPVA is used in formula.Vulcanizate is details
Can be such as table 1.
Embodiment 4
The method of embodiment 1 is repeated by each component content specified, but 2,4,6- Triaminopyrimidines are added in formula
0.2g, sulphur 2.5g, zinc diethyl dithiocarbamate 0.1g.Vulcanizate detailed performance such as table 1.
Embodiment 5
The method of embodiment 4 is repeated by each component content specified, but 30gPVA is added in formula.Vulcanizate is details
Can be such as table 1.
Embodiment 6
The method of embodiment 4 is repeated by each component content specified, but 40gPVA is added in formula.Vulcanizate is details
Can be such as table 1.
Embodiment 7
The method of embodiment 1 is repeated by each component content specified, but 40gPVA is added in formula, sulphur 2.5g, two
Zinc thiocarbamate 0.2g, zinc diethyl dithiocarbamate 0.3g.Vulcanizate detailed performance such as table 1.
Embodiment 8
The method of embodiment 7 is repeated by each component content specified, but 2,4,5,6- tetraminopyrimidines are added in formula
0.2g, 2,4,6- Triaminopyrimidine 0.4g.Vulcanizate detailed performance such as table 1.
Comparative example 1
By the method that each component content specified repeats to implement 3, but PVA and 2 is not used, 4,5,6- tetraminopyrimidines.Sulphur
Change glue detailed performance such as table 1.
Comparative example 2
By the method that each component content specified repeats to implement 3, but 2,4,5,6- tetraminopyrimidines are not used.Vulcanizate is detailed
Thin performance such as table 1.
Comparative example 3
By the method that each component content specified repeats to implement 3, but sulphur and any accelerator are not used.Vulcanizate is detailed
Performance such as table 1.
Comparative example 4
By the method that each component content specified repeats to implement 3, but charging sequence is first to add sulphur, next to that promoting
Agent, is finally aminated compounds.Vulcanizate detailed performance such as table 1.
Table 1
| Tensile strength (MPa) | Tearing strength (kN/m) | Self-healing properties (%) | Resilience (%) | |
| Embodiment 1 | 5.8 | 17.6 | 45 | 40 |
| Embodiment 2 | 8.9 | 20.1 | 57 | 48 |
| Embodiment 3 | 12.7 | 25.3 | 76 | 60 |
| Embodiment 4 | 4.9 | 15.3 | 40 | 36 |
| Embodiment 5 | 7.5 | 17.8 | 51 | 40 |
| Embodiment 6 | 10.3 | 22.4 | 65 | 52 |
| Embodiment 7 | 11.5 | 24.1 | 73 | 56 |
| Embodiment 8 | 11.2 | 23.9 | 71 | 54 |
| Comparative example 1 | 3.9 | 10.1 | 5 | 18 |
| Comparative example 2 | 4.3 | 12.3 | 25 | 23 |
| Comparative example 3 | 3.5 | 9.8 | 50 | 43 |
| Comparative example 4 | 5.3 | 14.1 | 28 | 34 |
The present invention utilizes emulsion dispersion, improves degrees of scatter of the PVA in XNBR, improves the mechanical strength of XNBR；Profit
Fracture and bonding process again with the hydrogen bond formed between PVA, prepare the XNBR vulcanizates with good self-reparing capability.Vulcanization
20~40gPVA is used in the every 100g rubber of glue, during 0.2~0.6g of aminated compounds, tensile strength ratio does not use PVA and amine
Compound highest increases by 330%, and, than not using PVA and aminated compounds highest increase by 150%, self-reparing capability is most for tearing strength
Height increases by 15 times, and resilience highest increases by 230%.The method can be widely used in all kinds of specific rubber products, be particularly well-suited to
Mechanical property requirements are high, the rubber of long service life.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, on the premise of the technology of the present invention principle is not departed from, some improvement and deformation can also be made, these improve and deform
Also should be regarded as protection scope of the present invention.
Claims (7)
1. a kind of XNBR vulcanization of rubber glue with self-healing properties, it is characterised in that including following components：The matter of XNBR 100
Amount part, the mass parts of PVA 20~40, the mass parts of aminated compounds 0.3~0.6, the aminated compounds is that 2,4,6- triamidos are phonetic
Pyridine, 2, one or two in 4,5,6- tetraminopyrimidines, the mass parts of vulcanizing agent 0.8~2.5, the mass of accelerator 0.1~0.5
Part.
2. a kind of XNBR vulcanization of rubber glue with self-healing properties according to claim 1, it is characterised in that：It is described
The matter average molecular weight of PVA is 95000~100000, and alcoholysis degree is 60%.
3. a kind of XNBR vulcanization of rubber glue with self-healing properties according to claim 1, it is characterised in that：The sulphur
Agent is sulphur, the accelerator be zinc dithiocarbamate, zinc diethyl dithiocarbamate in one or two.
4. the system of a kind of XNBR vulcanization of rubber glue with self-healing properties according to any one in claims 1 to 3
Preparation Method, it is characterised in that comprise the following steps：
Step one：PVA is weighed, 95 are added tooIn C deionized waters, stirring and dissolving, filtering, cooling obtains PVA solution；
Step 2：The PVA solution that step one is obtained is blended with XNBR latex, ultrasound, adds aminated compounds, vulcanization
Agent, accelerator, stirring, obtain PVA/XNBR mixed solutions, are poured into mould, dry obtain PVA/XNBR glue at room temperature
Film；
Step 3：The PVA/XNBR glued membranes that step 2 is obtained sulfidization molding in an oven, obtains with self-healing properties
XNBR vulcanization of rubber glue.
5. a kind of preparation method of XNBR vulcanization of rubber glue with self-healing properties according to claim 4, its feature
It is：Ultrasonic time is 0.5~1 hour in the step 2, and ultrasonic power is 125~250W, and temperature is 20~60 DEG C.
6. a kind of preparation method of XNBR vulcanization of rubber glue with self-healing properties according to claim 4, its feature
It is：The aminated compounds, vulcanizing agent, the addition sequence of accelerator are vulcanizing agent, aminated compounds, accelerator, are often added
The interval time of one class material is 0.5h.
7. a kind of preparation method of XNBR vulcanization of rubber glue with self-healing properties according to claim 4, its feature
It is：In the step 3, curing temperature is 60oC, the time is 20min.
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| CN201610244284.8A CN105860174B (en) | 2016-04-19 | 2016-04-19 | A kind of XNBR vulcanization of rubber glue with self-healing properties and preparation method thereof |
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Inventor after: Wang Jingyi Inventor after: Jia Hongbing Inventor after: Hang Zusheng Inventor after: Wang Zhangzhong Inventor after: Yu Lei Inventor after: Zhang Shiqing Inventor before: Wang Jingyi Inventor before: Jia Hongbing Inventor before: Xiao Hui Inventor before: Hang Zusheng Inventor before: Huang Chunhui Inventor before: Wang Yidi Inventor before: Guo Fei Inventor before: Wang Zhangzhong Inventor before: Yang Yiming |
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Effective date of registration: 20171127 Address after: 242000 Anhui Province, Xuancheng economic and Technological Development Zone, the new road in the south, Bai Jian Road West Patentee after: Xuancheng Hui Yuan Mstar Technology Ltd Address before: 1 No. 211167 Jiangsu city of Nanjing province Jiangning Science Park Hongjing Road Patentee before: Nanjing Institute of Technology |
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