CN106866844B - The method that emulsion method prepares hydrogenation natural gum - Google Patents
The method that emulsion method prepares hydrogenation natural gum Download PDFInfo
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- CN106866844B CN106866844B CN201710130786.2A CN201710130786A CN106866844B CN 106866844 B CN106866844 B CN 106866844B CN 201710130786 A CN201710130786 A CN 201710130786A CN 106866844 B CN106866844 B CN 106866844B
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- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
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Abstract
The present invention relates to a kind of methods that emulsion method prepares hydrogenation natural gum, and the natural gum in Heveatex is carried out hydrogenation modification using hydrazine hydrate/hydrogen peroxide/boric acid catalysis system, then uses 2%CaCl2It is dry after aqueous solution flocculation, prepare the hydrogenation natural gum (HNR) of different hydrogenation degrees.The catalyst system and catalyzing can be catalyzed NR main chains in emulsion state and add hydrogen；Gel content and decomposition temperature increase with the increase of NR hydrogenation degrees, and glass transition temperature is slightly increased；The crosslink density of vulcanizate increases as hydrogenation degree increases.After showing hydrogenation, the compliance of HNR reduces, and thermal stability improves；Degree of hydrogenation increases, and the crystallizing power of HNR declines.It is expected that the hydrogenation of NR is conducive to improve its ageing-resistant performance.
Description
Technical field
The present invention relates to a kind of modified natural rubber and the methods for being used to prepare modified natural rubber, more particularly, this hair
It is bright to be related to through emulsion method modified natural rubber method.
Background technology
Natural rubber is widely used in all trades and professions as a kind of natural green raw material, and product elasticity is big, breaks
Elongation is high, and mechanical stability is high, due in natural gum strand containing the active carbon-carbon double bond of chemical property, easily by
The effect of heat, oxygen, ozone, light etc. crosslinks or chain-breaking reaction, so as to influence the performance of rubber.Therefore people are not using
Chemical modification is carried out to natural rubber molecular structure with method, e.g., epoxy bond (- C- is introduced on the unsaturated double-bond of strand
O-C-) and a small amount of C=O bond (- C=O), prepare with excellent air-tightness, adhesiveness, resistance to wet skidding performance and good oil resistant
The epoxy natural rubber of property；Prepare chlorinated natural rubber by chlorination modified, with excellent adhesiveness, weatherability,
Wearability, corrosion resistance and anti-flammability etc.；The cyclization induced by carbocation, the cyclized hatural rubber obtained are mainly applied
In coatings industry and as adhesive and easer, the reinforcing agent of sole masterbatch is also acted as.
In recent years, people is caused to pay close attention to NR molecular carbon carbon double bond structure direct hydrogenations, the NR of partial hydrogenation, structure class
Like ethylene propylene diene rubber (EPDM).Since EPDM molecular structures are without polar substituent, intermolecular cohesive energy is relatively low, can be wider
Rubber is made to keep compliance in temperature range.It is many excellent that saturability and nonpolarity in structure have ethylene propylene diene rubber
Performance, such as excellent resistance to ozone aging, heat-proof aging, weather-resistant, acid and alkali-resistance, the water resistance of brilliance and excellent electrical isolation
Performance etc..The NR of hydrogen is added not only to show the characteristic of EPDM but also maintained the excellent properties of NR, is a kind of novel green rubber.
At present to NR plus hydrogen research, it is concentrated mainly on reaction mechanism and kinetics；Its HNR hydrogenation degree prepared
Up to 48%.It is difficult to be made the HNR of higher hydrogen degree.
Invention content
The goal of the invention of the present invention is to solve the problems, such as the HNR for being difficult to that high hydrogenation degree is made in the prior art, provides one
The method that kind emulsion method prepares hydrogenation natural gum, this method HNR hydrogenation degrees reach as high as 90%.
The following chemical equation of process of hydrogenation of the present invention：In hydrogenation reaction, by changing matching for catalyst system and catalyzing
Than control plus hydrogen degree, although being that H is added dropwise in reaction process2O2Into reaction system, but due to H2O2With extremely strong oxidation
Property, it is easily created hydroxyl radical free radical (HO) and hydrazine hydrate generation imidodicarbonic diamide (N2H2), such as reaction equation (1) institute in Fig. 4
Show；Reaction equation (2) represents NR hydrogenation processes；By (3) it is found that in hydrogenation process, the meeting of HO free radicals is simultaneously on attack C atoms
Active H atom is crosslinked between the macromolecular radical of generation, such as reaction equation (4).So with the intensification of degree of hydrogenation,
H2O2Amount it is more, the macromolecular radical of generation is more, and crosslinking therebetween is more, and gel content is bigger.
The present invention adopts the following technical scheme that：
A kind of method that emulsion method prepares hydrogenation natural gum improves hydrogenation degree by the way of intermittent addition reactant,
It is as follows：
Heveatex is heated to 45-75 DEG C under stiring, adds in hydrazine hydrate at this time；A certain amount of boric acid is weighed, to go
It is added in after ion water dissolution；Suitable H is added dropwise in constant speed2O2To reaction system is arrived, the reaction was continued after 7h is dripped off 1h, stopping reaction；Its
C=C double bonds, hydrazine hydrate and H in middle Heveatex NR2O2Molar ratio be 1：1-8：1-10, boric acid addition are 0.1-
0.3mol；It takes out reactant to be demulsified with 2% calcium chloride water, HNR raw rubbers is made.
Further, hydrogenated products are washed with deionized, is dried in vacuo in 60 DEG C of baking ovens for 24 hours, HNR raw rubbers is made.HNR
Hydrogenation degree is up to 90%.
More specific technical solution is：A kind of method that emulsion method prepares hydrogenation natural gum is reacted using intermittent add in
The mode of object improves hydrogenation degree, is as follows：
Heveatex is added in toward the four-hole boiling flask with condenser pipe, mechanical agitator and thermometer, opens mechanical agitation
Paddle, heating latex add in hydrazine hydrate at this time to 55 DEG C；A certain amount of boric acid is accurately weighed, to be added to after deionized water dissolving
In reaction system；Suitable H is added dropwise in constant speed2O2To reaction system is arrived, the reaction was continued after 7h is dripped off 1h, stopping reaction.Take out reaction
Object is demulsified with 2% calcium chloride water, and hydrogenated products are washed with deionized, and is dried in vacuo for 24 hours, is made in 60 DEG C of baking ovens
HNR raw rubbers.C=C in wherein NR:N2H4:H2O2Molar ratio is 1：1-6：1-8, boric acid addition are 0.1M.
Description of the drawings
The hydrogenation degree that Fig. 1 is the present invention is 17.6%, 34.6%, 42.7%, the HNMR spectrograms of 66% HNR and NR.
Fig. 2 is the infrared spectrum of above-mentioned HNR and NR.
Fig. 3 is measures above-mentioned NR and HNR gel contents curve graph using soxhlet extraction methods respectively.
Figure 4 and 5 are to be thermally decomposed using the starting degradation temperature (Tid) and most fast degradation temperature (Tmax) of the TGA HNR tested
Temperature and the glass transition temperature (Tg) that HNR is measured by DSC.
When Fig. 6 is -25 DEG C, NR and the HNR volume in dilatometer change over time curve.
Specific embodiment
In the following with reference to the drawings and specific embodiments, the present invention is further explained.It should be understood that these embodiments are merely to illustrate
The present invention rather than limit the scope of the invention.In addition, it should also be understood that, after the content that the present invention lectures is read, ability
Field technique personnel can make the present invention various changes or modification, and such equivalent forms also belong to the application appended claims
Book limited range.
Raw material used in the present invention：
Heveatex, dry rubber content 60% (mass fraction, similarly hereinafter), three Industrial Co., Ltd. of Shanghai.
Hydrazine hydrate, mass fraction 80%, Tianjin are won up to your dilute chemical reagent factory.
Hydrogen peroxide, mass fraction 30%, Beijing Chemical Plant.
Boric acid, mass fraction 99.8%, Beijing Yi Li fine chemicals Co., Ltd.
Detecting instrument used in the embodiment of the present invention：
The microcosmic knot of 400 type Nuclear Magnetic Resonance of AV analysis NR and HNR samples that HNMR Bruker companies of Germany produce
Structure；Its hydrogenation degree is calculated by the nmr spectrum of HNR.
The 27 type FTIR of Tensor that FTIR is produced with Bruker companies of Germany carry out infrared attenuation full reflection analysis to HNR,
To study the variation that natural rubber adds strand microstructure before and after hydrogen.
Thermogravimetric analysis (TGA) analyzes HNR raw rubbers with the TGA instrument that Mettler Toledo companies produce, nitrogen gas
Atmosphere, 10 DEG C/min of heating rate.
Differential scanning calorimetric (DSC) analyzes HNR with the DSC instrument that Mettler Toledo companies produce, nitrogen gas
Atmosphere, 10 DEG C/min of heating rate.
Detection method used in the present invention：
Soxhlet extraction methods measure HNR glue gel contents
The sample and m that quality is m are weighed respectively1Strainer, the strainer packet equipped with sample is put into extracting barrel, injects toluene,
Sample packet is made to be completely submerged in toluene.Extractor each section is connected, condensed water flow is connected, 24 is stripped in silicone oil bath
Hour, 135 DEG C of silicone oil bath temperature after extracting, takes out strainer packet, drying, weigh to obtain m2.Gel content w calculation formula are：
W=[(m2-m1)/m] * 100%
Dilatometric method surveys the low temperature crystallization performance of HNR
0.3-0.5gHNR raw rubbers are cut, its density is surveyed with assay balance method, it is small that sample is vacuumized at 50 DEG C to heating half
When, eliminate thermal history.Sample is fitted into dilatometer, then adding in mercury makes the mercury in capillary remember to certain altitude
Lower registration.By the temperature setting of high-low temperature test chamber at -25 DEG C, the dilatometer equipped with sample is put into wherein every one after stablizing
It fixes time and records registration, calculate volume change.
Embodiment 1：
Heveatex is added in toward the four-hole boiling flask with condenser pipe, mechanical agitator and thermometer, opens mechanical agitation
Paddle, heating latex add in hydrazine hydrate at this time to 55 DEG C；A certain amount of boric acid is accurately weighed, to be added to after deionized water dissolving
In reaction system；Suitable H is added dropwise in constant speed2O2To reaction system is arrived, the reaction was continued after 7h is dripped off 1h, stopping reaction.C=in NR
C:N2H4:H2O2Molar ratio is 1：1：1, boric acid addition is 0.1M.It takes out reactant to be demulsified with 2% calcium chloride water, spend
Ion water washing hydrogenated products, are dried in vacuo for 24 hours in 60 DEG C of baking ovens, and obtained hydrogenation degree is：17.6% HNR raw rubbers.
Embodiment 2：
Heveatex is added in toward the four-hole boiling flask with condenser pipe, mechanical agitator and thermometer, opens mechanical agitation
Paddle, heating latex add in hydrazine hydrate at this time to 55 DEG C；A certain amount of boric acid is accurately weighed, to be added to after deionized water dissolving
In reaction system；Suitable H is added dropwise in constant speed2O2To reaction system is arrived, the reaction was continued after 7h is dripped off 1h, stopping reaction.C=in NR
C:N2H4:H2O2Molar ratio is 1：2：1.5, boric acid addition is 0.1M.It takes out reactant to be demulsified with 2% calcium chloride water, use
Deionized water washs hydrogenated products, and the HNR raw rubbers for for 24 hours, being made that hydrogenation degree is 34.6% are dried in vacuo in 60 DEG C of baking ovens.
Embodiment 3：
Heveatex is added in toward the four-hole boiling flask with condenser pipe, mechanical agitator and thermometer, opens mechanical agitation
Paddle, heating latex add in hydrazine hydrate at this time to 55 DEG C；A certain amount of boric acid is accurately weighed, to be added to after deionized water dissolving
In reaction system；Suitable H is added dropwise in constant speed2O2To reaction system is arrived, the reaction was continued after 7h is dripped off 1h, stopping reaction.C=in NR
C:N2H4:H2O2Molar ratio is 1：3：4.5, boric acid addition is taken out reactant for 0.1M and is demulsified with 2% calcium chloride water, is used
Deionized water washs hydrogenated products, and the HNR raw rubbers for for 24 hours, being made that hydrogenation degree is 42.7% are dried in vacuo in 60 DEG C of baking ovens.
Embodiment 4：
Heveatex is added in toward the four-hole boiling flask with condenser pipe, mechanical agitator and thermometer, opens mechanical agitation
Paddle, heating latex add in hydrazine hydrate at this time to 55 DEG C；A certain amount of boric acid is accurately weighed, to be added to after deionized water dissolving
In reaction system；Suitable H is added dropwise in constant speed2O2To reaction system is arrived, the reaction was continued after 7h is dripped off 1h, stopping reaction.C=in NR
C:N2H4:H2O2Molar ratio is 1：4：5.25, boric acid addition is 0.1M.Reactant is taken out to be demulsified with 2% calcium chloride water,
Hydrogenated products are washed with deionized, the HNR raw rubbers for for 24 hours, being made that hydrogenation degree is 66.9% are dried in vacuo in 60 DEG C of baking ovens.
Embodiment 5：
Heveatex is added in toward the four-hole boiling flask with condenser pipe, mechanical agitator and thermometer, opens mechanical agitation
Paddle, heating latex add in hydrazine hydrate at this time to 55 DEG C；A certain amount of boric acid is accurately weighed, to be added to after deionized water dissolving
In reaction system；Suitable H is added dropwise in constant speed2O2To reaction system is arrived, the reaction was continued after 7h is dripped off 1h, stopping reaction.C=in NR
C:N2H4:H2O2Molar ratio is 1：6：8, boric acid addition is 0.2M.It takes out reactant to be demulsified with 2% calcium chloride water, spend
Ion water washing hydrogenated products are dried in vacuo the HNR raw rubbers for for 24 hours, being made that hydrogenation degree is 88.2% in 60 DEG C of baking ovens.
Embodiment 6：
Heveatex is added in toward the four-hole boiling flask with condenser pipe, mechanical agitator and thermometer, opens mechanical agitation
Paddle, heating latex add in hydrazine hydrate at this time to 55 DEG C；A certain amount of boric acid is accurately weighed, to be added to after deionized water dissolving
In reaction system；Suitable H is added dropwise in constant speed2O2To reaction system is arrived, the reaction was continued after 7h is dripped off 1h, stopping reaction.C=in NR
C:N2H4:H2O2Molar ratio is 1：6：10, boric acid addition is 0.2M.It takes out reactant to be demulsified with 2% calcium chloride water, use
Deionized water washs hydrogenated products, and the HNR raw rubbers for for 24 hours, being made that hydrogenation degree is 89.5% are dried in vacuo in 60 DEG C of baking ovens.
The study found that when hydrogenating Heveatex using hydrazine hydrate/hydrogen peroxide/boric acid catalyst system, in the presence of boric acid
Under, hydrazine hydrate reacts generation hydride presoma imidodicarbonic diamide with hydrogen peroxide, and imidodicarbonic diamide can be catalyzed carbon-carbon double bond in NR latex
Hydrogenation reaction, gained hydrogenation degree be 17.6%, 34.6%, 42.7%, the HNMR spectrograms of 66% HNR and NR are as shown in Figure 1.
It can be seen from Fig. 1 that the chemical shift of NR unsaturated olefin H proton peaks is at 5.2ppm, methylene H proton peaks and methyl H proton peaks
Chemical shift is respectively at 2.01ppm and 1.7ppm；With the increase of hydrogenation degree, insatiable hunger of the HNR chemical shifts at 5.2ppm
Become smaller with alkene H proton peak areas, illustrate that unsaturated carbon-carbon double bond is gradually reduced to the carbon-carbon single bond structure of saturation.In Fig. 1
Dashed region generates new saturation methyl and methylene H proton peaks for chemical shift after hydrogenation reaction at 0.8-1.2ppm.
The infrared spectrum of HNR and NR is shown in Fig. 2.1663cm-1And 737cm-1Respectively-C=C- stretching vibration peaks and methylene
Base (- CH2) stretching vibration peak, 836cm-1Locate as alkene=C-H Different Plane rocking vibrations peak；As HNR hydrogenation degrees increase
Greatly, unsaturated C=C double bonds 1663cm-1Absorption peak and 836cm-1The band area of alkene=C-H absorption peaks reduces, 737cm-1(-
CH2) at characteristic absorption peak become larger, illustrate that C=C is unfolded into polyethylene segment.
Measure NR and HNR gel contents respectively using soxhlet extraction methods, as shown in figure 3, with the increase of hydrogenation degree, HNR
Gel content general trend is increased.Not plus the NR dry glues of hydrogen are in itself containing 13% or so gel, when hydrogenation degree reaches
When 66.9%, gel content 34.4%.
Using the starting degradation temperature (T of the HNR of TGA testsid) and most fast degradation temperature (Tmax) heat decomposition temperature and by
DSC measures the glass transition temperature (Tg) of HNR, such as Fig. 4,5.With the increase of degree of hydrogenation it can be seen from Fig. 4 and table 1,
The T of HNRidIt is higher and higher, and NR is above, dotted line represents the T of HNRmaxIn raising trend.This is absolutely proved plus hydrogen makes shakiness
Fixed C=C keys are converted into more stable C-C keys, the enhancing of strand thermal stability.By the DSC curve of Fig. 5 it is found that the Tg of NR for-
65.11 DEG C, with the variation of hydrogenation degree, the Tg of HNR is slightly increased, this explanation with the reduction of number of double bonds, molecule it is submissive
Property is decreased slightly as low, NR resistance to low temperatures is influenced little.
The glass transition temperature and melting temperature of table 1.HNR samples
| Sample | Tid/℃ | Tmax/℃ | Tg/℃ |
| Pure NR | 302 | 379 | -65.11 |
| 17.6%HNR | 317 | 385 | -65.10 |
| 34.6%HNR | 325 | 393 | -64.98 |
| 42.7%HNR | 336 | 408 | -64.86 |
| 66.9%HNR | 334 | 406 | -64.32 |
Temperature-induced crystallization can occur between -50 DEG C to 10 DEG C for NR, and -25 DEG C or so, NR crystallization rates are most fast, and NR's is low
Warm crystallinity influences its application in tread rubber, and it is one of major measure for improving its lower temperature resistance to reduce crystallization temperature.-25
DEG C when, NR and the HNR volume in dilatometer change over time curve as shown in fig. 6, it will be appreciated from fig. 6 that the body of NR, 17.6%HNR
Product-time graph is the typical type of falling S, illustrates both glue at -25 DEG C, and as time went on, sample volume becomes smaller, crystallization
It is formed；The time of half is occurred using crystallization to characterize the speed of crystallization, that is, crystallizes half period t1/2, NR and hydrogenation degree are
17.6% HNR crystallization half periods are respectively for 7h, 140h；Hydrogenation degree is that the volume of 34.6% and 42.7% HNR exists respectively
Start slowly to become smaller after about 33h and 167h, show that crystallization starts, but until 500 hours curves are not also gentle, illustrate to crystallize not
Up to stabilization.And the volume of 66.9%HNR did not almost change in 500 hours, illustrated that temperature-induced knot does not almost occur for it
It is brilliant.From the point of view of macromolecular structure, chemical constitution is simpler, and strand is more regular, easier crystallization；With the increase of degree of hydrogenation, NR
The opening of middle C=C double bonds may be it is unordered, it is non-uniform so that original regular molecular chain is disturbed, and is formed after hydrogenation
Part second propylene structure and remaining unsaturated isoprene unit random distribution influence the regularity of NR, HNR crystallizing powers
It reduces.
Using hydrazine hydrate/hydrogen peroxide/boric acid system and its dosage is adjusted, highest can prepare 89.5% hydrogenation in NR latex
The HNR of degree.HNR gel contents increase with hydrogenation degree and are increased, and thermal stability improves；Glass transition temperature Tg increases with hydrogenation degree
It is big slightly to increase, illustrate plus hydrogen is little on the influence of its lower temperature resistance.At -25 DEG C, HNR degrees of hydrogenation are higher, and crystal property is poorer.Sulphur
The crosslink density for changing glue increases with the increase of hydrogenation degree.
Claims (3)
1. a kind of method that emulsion method prepares hydrogenation natural gum improves hydrogenation degree by the way of intermittent addition reactant, has
Body step is as follows：Heveatex is heated to 45-75 DEG C under stiring, adds in hydrazine hydrate at this time；A certain amount of boric acid is weighed, with
It is added in after deionized water dissolving；Suitable H is added dropwise in constant speed2O2To reaction system, the reaction was continued after 7h is dripped off 1 h, stopping reaction；
C=C double bonds, hydrazine hydrate and H in wherein Heveatex NR2O2Molar ratio be 1：1-8：1-10, boric acid addition are 0.1-
0.3mol；It takes out reactant to be demulsified with 2% calcium chloride water, HNR raw rubbers is made.
2. according to the method described in claim 1, it is characterized in that：It is made to further include in HNR raw rubber steps and be washed with deionized water
Hydrogenated products are washed, are dried in vacuo for 24 hours in 60 DEG C of baking ovens.
3. according to the method described in claim 1, it is characterized in that：HNR hydrogenation degrees are up to 90%.
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| CN113816393B (en) * | 2021-10-19 | 2023-03-17 | 青海利亚达化工有限公司 | Iron removal method for preparing high-purity boric acid |
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| US4452950A (en) * | 1983-02-22 | 1984-06-05 | The Goodyear Tire & Rubber Company | Process for hydrogenation of carbon-carbon double bonds in an unsaturated polymer in latex form |
| CN102617901A (en) * | 2012-03-22 | 2012-08-01 | 北京化工大学 | Application of hydrogenated nitrile latex |
| 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 |
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| US4452950A (en) * | 1983-02-22 | 1984-06-05 | The Goodyear Tire & Rubber Company | Process for hydrogenation of carbon-carbon double bonds in an unsaturated polymer in latex form |
| CN102617901A (en) * | 2012-03-22 | 2012-08-01 | 北京化工大学 | Application of hydrogenated nitrile latex |
| 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 |
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