CN106478924B - A kind of hydrogenated butyronitrile type polyurethane of crosslinking - Google Patents
A kind of hydrogenated butyronitrile type polyurethane of crosslinking Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
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- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
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- C08C19/06—Epoxidation
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- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
- C08C19/34—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with oxygen or oxygen-containing groups
- C08C19/40—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with oxygen or oxygen-containing groups with epoxy radicals
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
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- C08G18/3802—Low-molecular-weight compounds having heteroatoms other than oxygen having halogens
- C08G18/3804—Polyhydroxy compounds
- C08G18/3806—Polyhydroxy compounds having chlorine and/or bromine atoms
- C08G18/3808—Polyhydroxy compounds having chlorine and/or bromine atoms having chlorine atoms
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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Abstract
The present invention provides a kind of hydrogenated butyronitrile type polyurethane of crosslinking, is to be formed by polyfunctionality hydrogenation hydroxyl terminated butyl nitrile (HTBN) rubber with isocyanate-crosslinked；The polyfunctionality hydrogenation hydroxyl terminated butyl nitrile (HTBN) rubber is to recycle carboxylic acid to introduce hydroxyl to PART EPOXY group open loop and obtain by introducing epoxy group in terminal hydroxy liquid hydrogenated nitrile-butadiene rubber.The present invention also provides a kind of preparation methods of the hydrogenated butyronitrile type polyurethane of crosslinking.The hydrogenated butyronitrile type polyurethane of novel crosslinking proposed by the present invention overcomes the not high disadvantage of butyronitrile type polyurethane loss of properties on aging and mechanical strength.Pass through the measurement of swelling ratio and gel fraction, it was demonstrated that introduce chemical crossbond in polyurethane, the introducing of chemical crossbond also overcomes polyurethane when leading to high temperature due to a lack of chemical crossbond the shortcomings that poor mechanical property.
Description
Technical field
The invention belongs to high-molecular organic material fields, and in particular to a kind of the hydrogenated butyronitrile type polyurethane and its system of crosslinking
Preparation Method.
Background technique
The raw material for preparing of polyurethane includes oligomer polyol, chain extender and polyisocyanates.Oligomer polyol includes
Polyester polyol, polyether polyol, polyolefin polyhydric alcohol and other oligomer polyols.The poly- fourth of terminal hydroxy group in polyolefin polyhydric alcohol
Elastomer abbreviation hydroxy'terminated butadiene nitrile rubber (HTBN) made of Butadiene-acrylonitrile.
Butyronitrile type polyurethane has superior hydrolytic resistance and low-temperature flexibility, but because containing a large amount of carbon in its strand
The unsaturated structure of carbon double bond keeps its ozone-resistant aging property poor, influences the performance of product when used for a long time.Compared to polyester
The polyurethane of polyalcohol synthesis, butyronitrile type polyurethane is because its soft segment partial skeleton is hydrocarbon backbone, so the mechanical property of product
It is not high, limit being widely used for butyronitrile type polyurethane.
Hydrogenation modification is the modified a kind of common method of unsaturated polymer, so this laboratory is with this method, it is right
Hydroxyl terminated butyl nitrile (HTBN) rubber (HTBN) glue carries out hydrogenation modification, synthesizes a kind of not double bond containing terminal hydroxy liquid hydrogenation fourth of main chain
Nitrile rubber (HHTBN) makes product obtain superior ozone-resistant aging property with its synthesis of polyurethane.The application attempts again
Epoxy group is introduced in HHTBN, and the carboxylic acid compound open loop of PART EPOXY group makes to introduce a part of hydroxyl in strand
Base obtains the HHTBN of polyfunctionality, so that the polyurethane of synthesis is had a small amount of cross-bond, obtains the heat resistance of polyurethane
A degree of raising.Remaining this polar group of a large amount of epoxy group in strand, and to the mechanical property of polyurethane
Raising with oil resistance has served very important.
Summary of the invention
It is an object of the invention to overcome the performance deficiency of existing butyronitrile type polyurethane, from raw material hydroxyl terminated butyl nitrile (HTBN)
It is structurally-modified to set out, so that the polyurethane of synthesis is had following structure feature, does not contain carbon-carbon double bond in strand, contain epoxy group
Group, and contain chemical crossbond.So the invention proposes the friendships of a kind of ozone and aging resistance, oil resistant and excellent in mechanical performance
Join type polyurethane.
Realize above-mentioned purpose technical solution of the present invention are as follows:
A kind of hydrogenated butyronitrile type polyurethane of crosslinking is to hydrogenate hydroxyl terminated butyl nitrile (HTBN) rubber (HHTBN) by polyfunctionality
It is formed with isocyanate-crosslinked.The polyfunctionality hydrogenation hydroxyl terminated butyl nitrile (HTBN) rubber is by hydrogenating fourth in terminal hydroxy liquid
Epoxy group is introduced in nitrile rubber, and carboxylic acid is recycled to introduce hydroxyl to PART EPOXY group open loop and obtain.
The present invention also proposes the preparation method of the hydrogenated butyronitrile type polyurethane of the crosslinking.
A kind of preparation method of the hydrogenated butyronitrile type polyurethane of crosslinking, comprising steps of
(1) it takes hydroxyl terminated butyl nitrile (HTBN) rubber (HTBN) to be dissolved in organic solvent, is configured to liquid nitrile rubber solution；Second
Acid and hydrogen peroxide are added to liquid nitrile rubber solution as epoxidation reagent, carry out epoxidation to HTBN at 50~70 DEG C
Reaction, carries out liquid separation for the mixed liquor after reaction, rotates, and drying obtains epoxidation hydroxyl terminated butyl nitrile (HTBN) rubber (EHTBN)；
(2) to double-bond hydrogenation and to epoxy group open loop: using Wilkinson catalyst and matching to the reaction of double-bond hydrogenation
Body triphenyl phosphine catalyst；With carboxylic acid to epoxy group open loop, the carboxylic acid be the monoacid of C2~10, C2~10 binary acid,
One of benzoic acid, phenylacetic acid are a variety of；
First to double-bond hydrogenation, then to epoxy group open loop, or first to epoxy group open loop, then to double-bond hydrogenation；
(3) it obtains product using step (2) to react with isocyanates, for temperature at 60~85 DEG C, the time is 2~4h, is obtained
Performed polymer, performed polymer are hot-forming with chain extender.
Further, in step (1), the mass ratio of hydroxyl terminated butyl nitrile (HTBN) rubber (HTBN) and acetic acid, hydrogen peroxide is 30:
20~40:80~90.Hydrogen peroxide used is the hydrogen peroxide of commercially available mass fraction 28~35%.
Wherein, in step (1) and step (2), the rubber reacted is dissolved in organic solvent and mass content 5~30% is made
Solution；The organic solvent is one of toluene, dimethylbenzene, ethylene glycol, acetone or a variety of.
Wherein, in step (1), pass through control reaction time control epoxidation hydroxyl terminated butyl nitrile (HTBN) rubber (EHTBN)
Epoxy content: the reaction time is 3~16h, and epoxy content is 5~35%, and the reaction time is longer, and epoxy content is higher.
Preferably, the reaction time is 7~10h, and epoxy content is 10~17%.
Wherein, the step (2) is in the reaction of double-bond hydrogenation, 90~140 DEG C of temperature, under 2~4MPa of Hydrogen Vapor Pressure, adds
Hydrogen reacts 6~10h,
The Wilkinson catalyst accounts for the epoxidation hydroxyl terminated butyl nitrile (HTBN) rubber (EHTBN) for carrying out double-bond hydrogenation reaction
Quality 0.2~1.5%, catalyst and triphenylphosphine ligand mass ratio are 1:1~1:8.
The rubber for carrying out double-bond hydrogenation reaction can be epoxidation hydroxyl terminated butyl nitrile (HTBN) rubber (EHTBN), be also possible to
With the hydroxyl terminated butyl nitrile (HTBN) rubber after carboxylic acid open loop.
Wherein, the step (2) is to the carboxylic acid and epoxidation hydrogenated butyronitrile rubber in the reaction of epoxy group open loop, being added
The molar ratio of glue epoxide epoxy group group is 0.5~5.0:1.
It is highly preferred that the step (2) is in the reaction of epoxy group open loop, 60~100 DEG C of reaction temperature, the time 3~
7h, the carboxylic acid are one of acetic acid, propionic acid, acrylic acid；The molar ratio of carboxylic acid and epoxy group is 1.0~3.0:1.
Wherein, in the step (3), the isocyanates is 2,4- diisocyanate, 2,6- diisocyanate, diphenyl
One of methane diisocyanate is a variety of；The chain extender is 3,5- dimethythiotoluene diamine, 1,4-butanediol, 3,3-
One of two chloro- 4,4- diaminodiphenyl-methanes.
In step (3), isocyanate content in performed polymer can be measured.The additional amount and isocyanate content of chain extender meet
Stoichiometric relationship, chain extender and isocyano molal quantity ratio are 2:1.
Performed polymer mixes at 55~65 DEG C with chain extender, the hot pressing at 100~120 DEG C.
The beneficial effects of the present invention are:
The hydrogenated butyronitrile type polyurethane of novel crosslinking proposed by the present invention overcomes butyronitrile type polyurethane loss of properties on aging
The not high disadvantage with mechanical strength.Pass through the measurement of swelling ratio and gel fraction, it was demonstrated that introduce chemical friendship in polyurethane
Join key, poor mechanical property that introducings of chemical crossbond also overcomes polyurethane when leading to high temperature due to a lack of chemical crossbond it is scarce
Point.So polyurethane proposed by the present invention is a kind of butyronitrile type polyurethane of the modification of excellent combination property, greatly widen
The application range of butyronitrile type polyurethane product.
Preparation method proposed by the present invention recycles carboxylic acid compound and portion by introducing epoxy group in HTBN
Divide epoxy group reaction, hydroxyl is introduced in strand.Ring-opening reaction introduces hydroxyl, not only compensates for because adding hydrogen to lead to hydroxyl value
It reduces, and the HHTBN of terminal hydroxy group is made to be converted to the HHTBN of polyfunctionality, and then the polyurethane of synthesis is made to form chemical crosslinking
Key, therefore the present invention realizes and is not required to additional small molecule crosslinking agent and can be obtained the purpose of cross-linked type polyurethane.And the present invention
In polyurethane be free of unsaturated carbon carbon bond, so the ozone-resistant aging property of polyurethane is excellent；The introducing of epoxy group makes again
It is with preferable mechanical property and oil resistance.So the present invention has prepared a kind of polyurethane of excellent combination property, pole
The big application range for having widened butyronitrile type polyurethane.
Detailed description of the invention
Fig. 1 be to the resulting product epoxidation terminal hydroxy liquid hydrogenated nitrile-butadiene rubber of step in Examples 1 to 5 (3), and
The nuclear-magnetism characterization that the resulting terminal hydroxy liquid hydrogenated nitrile-butadiene rubber of step (1) carries out in embodiment 6；
Fig. 2 is poly- ammonia synthesized by the HHTBN and step (5) to step in Examples 1 to 5 (4) resulting polyfunctionality
The resulting HHTBN of step (1) and the obtained polyurethane of step (2) carry out IR Characterization in ester and embodiment 6.
SEM after Fig. 3 is ozone aging 36h schemes, wherein the SEM figure that upper figure is butyronitrile type polyurethane ozone aging 36h, under
The SEM figure that figure is 3 gained cross-linking type hydrogenated butyronitrile type polyurethane ozone aging 36h of embodiment.
Specific embodiment
Following specific embodiments should not be construed as limiting the invention for illustrating the present invention.
In embodiment, unless otherwise instructed, technological means used is this field conventional technology.
Embodiment 1:
(1) it takes hydroxyl terminated butyl nitrile (HTBN) rubber (HTBN) to be dissolved in dimethylbenzene, is configured to the solution of mass fraction 10wt%；
Take the above-mentioned solution of 300g in 500ml there-necked flask, be added 29.88g acetic acid, then be added dropwise hydrogen peroxide solution (Aladdin reagent,
Mass fraction 30%) 84.66g, 4h is stirred to react at 65 DEG C.Mixed liquor after reaction is subjected to precipitating, is washed, drying obtains
Epoxidation hydroxyl terminated butyl nitrile (HTBN) rubber (EHTBN) detects through nuclear-magnetism and calculates epoxy content E%=7%.
(2) use dimethylbenzene as solvent, EHTBN be made into the glue that mass concentration is 10%, in a high pressure reaction kettle plus
Enter glue 250g, adds Wilkinson catalyst 0.2g, ligand triphenylphosphine 0.6g, 110 DEG C of temperature, Hydrogen Vapor Pressure 4MPa
Under, hydrogenation reaction 8h obtains terminal hydroxy liquid hydrogenated nitrile-butadiene rubber (E-HHTBN) solution containing epoxy group after reaction.
(3) take step (2) acquired solution 250g in 500ml there-necked flask, addition 4.5g acetic acid, 100 DEG C of temperature, the time
3h is rotated after reaction, and drying obtains the EHHTBN of polyfunctionality；
(4) it takes the product 20g of step (3) in the there-necked flask of 150ml, is dehydrated 2h under 110 DEG C of vacuumized conditions.Dehydration
After cool the temperature to 65 DEG C, 2,4- toluene di-isocyanate(TDI) (TDI) 4.20g is added, reacts and temperature is risen to 80 after 0.5h
DEG C, the reaction was continued, and 2.5h obtains performed polymer.The isocyanate content for measuring performed polymer is 5.73%.According to the different of performed polymer
Cyanic acid ester content weighs chain extender 3, and chloro- 4, the 4- diaminodiphenyl-methane (MOCA) of 3- bis- takes the MOCA for being preheated to liquid
2.73g and 15g performed polymer (chain extender and isocyano molal quantity ratio be 2:1) is uniformly mixed at 60 DEG C, is injected in grinding tool,
Hot pressing 20min obtains product in the flat-bed press that temperature is 110 DEG C.
Embodiment 2
Step (1) the epoxidation time is extended into 6h, other conditions remain unchanged to arrive the EHTBN of E%=10%；
The epoxy content of EHTBN is higher, and the product hydroxyl value for obtaining step (3) ring-opening reaction is higher；Therefore, pre-polymerization obtained by step (4)
The isocyanate content of body reduces, its value is 5.49% after measured, is calculated according to material proportion, MOCA mass, which need to be added, is
2.62g。
Other operations are the same as embodiment 1.
Embodiment 3
Step (1) the epoxidation time is extended into 8h, other conditions remain unchanged to arrive the EHTBN of E%=13%；
The epoxy content of EHTBN is higher, and the product hydroxyl value for obtaining step (3) ring-opening reaction is higher；Therefore, pre-polymerization obtained by step (4)
The isocyanate content of body reduces, its value is 4.89% after measured, is calculated according to material proportion, MOCA mass, which need to be added, is
2.33g。
Other operations are the same as embodiment 1.
Embodiment 4
Step (1) the epoxidation time is extended into 10h, other conditions remain unchanged to arrive the EHTBN of E%=17%；
The epoxy content of EHTBN is higher, and the product hydroxyl value for obtaining step (3) ring-opening reaction is higher；Therefore, pre-polymerization obtained by step (4)
The isocyanate content of the performed polymer of body reduces, its value is 4.71% after measured, is calculated according to material proportion, MOCA matter need to be added
Amount is 2.24g.
Other operations are the same as embodiment 1.
Embodiment 5
Step (1) the epoxidation time is extended into 13h, other conditions remain unchanged to arrive the EHTBN of E%=24%；
The epoxy content of EHTBN is higher, and the product hydroxyl value for obtaining step (3) ring-opening reaction is higher；Therefore, pre-polymerization obtained by step (4)
The isocyanate content of the performed polymer of body reduces, its value is 4.54% after measured, is calculated according to material proportion, MOCA matter need to be added
Amount is 2.16g.
Other operations are the same as embodiment 1.
Embodiment 6:
(1) it takes hydroxyl terminated butyl nitrile (HTBN) rubber (HTBN) to be dissolved in dimethylbenzene, is configured to the solution of mass fraction 15wt%；
It takes the above-mentioned solution of 300g in 500ml there-necked flask, 45g acetic acid is added, then hydrogen peroxide solution 130g is added dropwise, is stirred at 60 DEG C
React 7h.Mixed liquor after reaction is subjected to precipitating, is washed, drying obtains epoxidation hydroxyl terminated butyl nitrile (HTBN) rubber
(EHTBN), it is detected through nuclear-magnetism and calculates epoxy content E%=11%.
(2) it takes step (1) products therefrom to be dissolved in the solution that dimethylbenzene is made into 12wt%, 250g solution is placed in 500ml tri-
In mouth bottle, addition 45g acetic acid, 90 DEG C of temperature, time 4h.
(3) glue of step (2) is taken, glue 250g is added in a high pressure reaction kettle, adds Wilkinson catalyst
0.2g, ligand triphenylphosphine 0.6g, 110 DEG C of temperature, under Hydrogen Vapor Pressure 3MPa, hydrogenation reaction 8h obtains more officials after reaction
The EHHTBN of energy degree.
Other are by operation with embodiment 1.
Embodiment 7
(1) it takes hydroxyl terminated butyl nitrile (HTBN) rubber (HTBN) to be dissolved in dimethylbenzene, is configured to the liquid of mass fraction 10wt%
Nitrile rubber solution；It takes 250g glue in autoclave, adds Wilkinson catalyst 0.2g, ligand triphenylphosphine
0.6g, 110 DEG C of temperature, under Hydrogen Vapor Pressure 4MPa, hydrogenation reaction 8h is rotated after reaction, and drying obtains terminal hydroxy group liquid
Body hydrogenated nitrile-butadiene rubber (HHTBN).
(2) it takes the product 20g of step (1) in the there-necked flask of 150ml, is dehydrated 2h under 110 DEG C of vacuumized conditions.Dehydration
After cool the temperature to 65 DEG C, 2,4- toluene di-isocyanate(TDI) (TDI) 4.20g is added, reacts and temperature is risen to 80 after 0.5h
DEG C the reaction was continued, and 2.5h obtains performed polymer, and the isocyanate content for measuring performed polymer is 6.09%.
Chain extender is weighed according to the isocyanate content of performed polymer, takes chloro- 4, the 4- diamino of 3,3- bis- for being preheated to liquid
Diphenyl methane (MOCA) 2.90g is uniformly mixed at 60 DEG C with 15g performed polymer, is injected in grinding tool, is 110 DEG C flat in temperature
Hot pressing 20min obtains product in plate hot press.
Material characterization and discussion
To the resulting product epoxidation terminal hydroxy liquid hydrogenated nitrile-butadiene rubber of step in Examples 1 to 5 (2), and implement
The resulting terminal hydroxy liquid hydrogenated nitrile-butadiene rubber of step (1) has carried out nuclear-magnetism characterization, the result is shown in Figure 1 in example 7.2.52ppm for
The characteristic peak of hydrogen on the connected carbon of itrile group；2.76ppm and 2.92ppm is respectively the characteristic peak of cis and trans epoxy group, it is seen that
With the increase of epoxy content, characteristic peak enhancing at 2.76ppm and 2.92ppm；4.8~5.8ppm is the characteristic peak of carbon-carbon double bond,
The peak of liquid butyronitrile here after hydrogenation disappears, this turns out the hydrogenated butyronitrile liquid rubber for being successfully prepared different epoxy contents
Glue.
In Fig. 2, the infrared curve of the liquid nitrile rubber (HHTBN) of terminal hydroxy group is compared, the HHTBN of polyfunctionality exists
1735cm-1There is carbonyl characteristic peak in place, while in 3500cm-1Place's hydroxyl characteristic peak is remarkably reinforced, this illustrates that acetic acid is successfully beaten
Open loop oxygen groups introduce hydroxyl and ester group in HHTBN strand；In the infrared curve of polyurethane, 2270cm-1Place is not go out
Existing-NCO characteristic peak, and 3330cm-1Locate appearance-NH- absorption peak, 1660~1720cm-1There is the feature of-C=O- in urea groups
Peak illustrates successfully to prepare polyurethane elastomer, and the HHTBN-PU being crosslinked is in 889cm-1There is the characteristic peak of epoxy group in place, says
In the bright polyurethane for being successfully introduced into epoxy group, and in 915cm-1And 967cm-1The feature of carbon-carbon double bond is not observed in place
Peak illustrates that hydrogenation successfully eliminates the carbon carbon unsaturated double-bond in butyronitrile type polyurethane.
Fig. 3 shows the SEM figure after ozone aging 36h, wherein upper figure is the SEM of butyronitrile type polyurethane ozone aging 36h
Figure, the visible a large amount of crackles of sample surfaces this is because ozone is reacted with carbon-carbon double bond causes molecular chain rupture, and then go out sample
Existing crackle.The SEM that the following figure is 3 gained cross-linking type hydrogenated butyronitrile type polyurethane ozone aging 36h of embodiment schemes, and sample surfaces are smooth
Flawless shows excellent ozone-resistant aging property.
Comparative example 1
It takes the hydroxyl terminated butyl nitrile (HTBN) rubber of 20g in the there-necked flask of 150ml, is dehydrated 2h under 110 DEG C of vacuumized conditions.
By temperature liter after cooling the temperature to 65 DEG C, addition 2,4- toluene di-isocyanate(TDI) (TDI) 4.20g, reaction 0.5h after dehydration
To 80 DEG C, the reaction was continued that 2.5h obtains performed polymer, and the isocyanate content for measuring performed polymer is 5.96%.According to performed polymer
Isocyanate content weigh chain extender, take chloro- 4, the 4- diaminodiphenyl-methane (MOCA) of 3,3- bis- for being preheated to liquid
2.84g is uniformly mixed at 60 DEG C with 15g performed polymer, is injected in grinding tool, the hot pressing in the flat-bed press that temperature is 110 DEG C
20min obtains product.
The test result of table 1. embodiment of the present invention and comparative example rubber
The data of table 1 are compared and analyzed, phase homogenous quantities are added in the synthesis performed polymer stage in embodiment and comparative example
Liquid nitrile rubber and 2,4- diisocyanate, but the isocyanate content of gained performed polymer is mutually far short of what is expected, this is because
Examples 1 to 5 is by being introduced back into hydroxyl to epoxy group open loop on the basis of hydroxyl terminated butyl nitrile (HTBN), and epoxy content is got over
Height, open loop rate is higher under the conditions of identical ring-opening reaction, and the HHTBN hydroxy radical content of gained polyfunctionality is higher, so synthesis
Performed polymer process consumption isocyanates is more, and gained performed polymer is made to obtain isocyanate content reduction；Embodiment 7 is because of hydrogenation process
Reduce hydroxyl value slightly, so the isocyanate content of its performed polymer slightly increases.The size of swelling ratio Q can be used to measure friendship
Join the size of density, the present invention is the swelling ratio measured in n,N-Dimethylformamide (DMF), it can be seen that is utilized multifunctional
HHTBN synthesize polyurethane its crosslink density obviously increases.After sample reaches swelling equilibrium in DMF, pass through high temperature drying
Method remove gel in solvent to get arrive pure crosslinked, the ratio between quality and elastomer initial mass referred to as gel
Score G.The size of gel fraction reflects the degree of perfection of cross-linked network to a certain extent, is closed using polyfunctionality HHTBN
It is also to be greatly improved at its gel fraction of polyurethane is obtained, so illustrating that the present invention has synthesized a kind of hydrogenated butyronitrile of cross-linking type
Type polyurethane.
1 mechanical property of contrast table, embodiment 7 are to carry out hydrogenation treatment to polyurethane, are increased to its tensile strength
26.0MPa, elongation at break reach 499%, this is because the degree of order increases soft segment after hydrogenation, regular arrangement forms crystallization institute
It causes；Implement 1~5 and introduce epoxy group and chemical crossbond on the basis of hydrogenation, reaches mechanical property in epoxy content 13%
Most preferably, tensile strength doubles, and elongation at break also improves a lot.Epoxy content, which continues to increase, will will affect soft and hard segments
Microphase separation degree, mechanical property can decline again.Oil resistance data are compared, preparation method proposed by the invention is to poly- ammonia
Ester oil resistivity increases.
Above embodiment be only a specific embodiment of the invention is described, not to the scope of the present invention into
Row limits, and those skilled in the art can also do numerous modifications and variations on the basis of existing technology, set not departing from the present invention
Under the premise of meter spirit, all variations and modifications that this field ordinary engineering and technical personnel makes technical solution of the present invention,
It should fall within the scope of protection determined by the claims of the present invention.
Claims (8)
1. a kind of preparation method of the hydrogenated butyronitrile type polyurethane of crosslinking, which is characterized in that comprising steps of
(1) it takes hydroxyl terminated butyl nitrile (HTBN) rubber to be dissolved in organic solvent, is configured to liquid nitrile rubber solution；Take acetic acid and dioxygen
Water is added to liquid nitrile rubber solution as epoxidation reagent, carries out epoxidation reaction to HTBN at 50~70 DEG C, will be anti-
Mixed liquor after answering carries out liquid separation, rotates, and drying obtains epoxidation hydroxyl terminated butyl nitrile (HTBN) rubber；
(2) to double-bond hydrogenation and to epoxy group open loop: using Wilkinson catalyst and ligand three to the reaction of double-bond hydrogenation
Phenyl phosphine catalyst；With carboxylic acid to epoxy group open loop, in the reaction of epoxy group open loop, 60~100 DEG C of reaction temperature, the time
3~7h, the carboxylic acid are one of acetic acid, propionic acid, acrylic acid；The molar ratio of carboxylic acid and epoxy group is 1.0~3.0:1；
First to double-bond hydrogenation, then to epoxy group open loop, or first to epoxy group open loop, then to double-bond hydrogenation；
(3) it obtains product using step (2) to react with isocyanates, for temperature at 60~85 DEG C, the time is 2~4h, obtains pre-polymerization
Body, performed polymer are hot-forming with chain extender.
2. preparation method according to claim 1, which is characterized in that in step (1), hydroxyl terminated butyl nitrile (HTBN) rubber and second
Sour, hydrogen peroxide mass ratio is 30:20~40:80~90.
3. preparation method according to claim 1, which is characterized in that in step (1) and step (2), the rubber that is reacted
The solution of mass content 5~30% is made in organic solvent for peptization；The organic solvent is toluene, dimethylbenzene, ethylene glycol, acetone
One of or it is a variety of.
4. preparation method according to claim 1, which is characterized in that in step (1), by controlling reaction time control ring
Aoxidize the epoxy content of hydroxyl terminated butyl nitrile (HTBN) rubber: the reaction time is 3~16h, and epoxy content is 5~35%.
5. the preparation method according to claim 4, which is characterized in that the reaction time be 7~10h, epoxy content be 10~
17%.
6. preparation method according to claim 1, which is characterized in that the step (2) is in the reaction of double-bond hydrogenation, temperature
90~140 DEG C of degree, under 2~4MPa of Hydrogen Vapor Pressure, 6~10h of hydrogenation reaction；
The Wilkinson catalyst accounts for the rubber quality 0.2~1.5% for carrying out double-bond hydrogenation reaction, catalyst and triphenylphosphine
It is 1:1~1:8 with body mass ratio.
7. preparation method according to claim 1, which is characterized in that reaction of the step (2) to epoxy group open loop
In, the molar ratio of the carboxylic acid and epoxidation hydrogenated nitrile-butadiene rubber epoxide epoxy group group that are added is 0.5~5.0:1.
8. described in any item preparation methods according to claim 1~7, which is characterized in that in the step (3), the isocyanide
Acid esters is 2,4- toluene di-isocyanate(TDI), one of methyl diphenylene diisocyanate or a variety of；The chain extender is 3,5-
Dimethythiotoluene diamine, 1,4-butanediol, 3,3 '-two chloro- 4, one of 4 '-diaminodiphenyl-methanes；
Performed polymer mixes at 55~65 DEG C with chain extender, the hot pressing at 100~120 DEG C.
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| CN104231118A (en) * | 2014-09-15 | 2014-12-24 | 北京化工大学 | Hydrogenated hydroxyl-terminated liquid nitrile-butadiene rubber and preparation method thereof |
| CN105175683A (en) * | 2015-10-12 | 2015-12-23 | 苏州法斯特信息科技有限公司 | Oil-resistant and heat-resistant cross-linking type ammonia ester elastomer composite and preparation method thereof |
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