CN106866844A - 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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- CN106866844A CN106866844A CN201710130786.2A CN201710130786A CN106866844A CN 106866844 A CN106866844 A CN 106866844A CN 201710130786 A CN201710130786 A CN 201710130786A CN 106866844 A CN106866844 A CN 106866844A
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- hydrogenation
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- natural gum
- boric acid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/02—Hydrogenation
Abstract
The present invention relates to a kind of method that emulsion method prepares hydrogenation natural gum, the natural gum in Heveatex is carried out by hydrogenation modification using hydrazine hydrate/hydrogen peroxide/boric acid catalysis system, then use 2%CaCl2Dried after aqueous solution flocculation, prepared the hydrogenation natural gum (HNR) of different hydrogenation degrees.The catalyst system and catalyzing can be in emulsion state catalysis NR main chain hydrogenation；Gel content and decomposition temperature increase with the increase of NR hydrogenation degrees, and glass transition temperature slightly has and raised；The crosslink density of vulcanizate increases as hydrogenation degree increases.After showing hydrogenation, the compliance reduction of HNR, heat endurance is improved；Degree of hydrogenation increases, and the crystallizing power of HNR declines.The hydrogenation of estimated NR is conducive to improving its ageing-resistant performance.
Description
Technical field
A kind of method the present invention relates to modified natural rubber and for preparing modified natural rubber, more particularly, this hair
It is bright to be related to by 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 its product elasticity is big, break
Elongation is high, and mechanical stability is high, due to, containing the active carbon-carbon double bond of chemical property, being easily subject in natural gum strand
The effect of heat, oxygen, ozone, light etc. is crosslinked 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, cohesive, resistance to wet skidding performance and good oil resistant
The epoxy natural rubber of property；Prepare chlorinated natural rubber by chlorination modified, its have excellent adhesiveness, weatherability,
Wearability, corrosion resistance and anti-flammability etc.；The cyclization induced by carbocation, the cyclized hatural rubber for drawing mainly is applied
In coatings industry and as adhesive and easer, the reinforcing agent of sole masterbatch is also acted as.
In recent years, people are caused to pay close attention to NR molecular carbon carbon double bond structure direct hydrogenations, the NR of partial hydrogenation, its structure class
Like ethylene propylene diene rubber (EPDM).Because EPDM molecular structures are free of polar substituent, intermolecular cohesive energy is relatively low, can be wider
Rubber is set to keep compliance in temperature range.Saturability in structure and nonpolar to have ethylene propylene diene rubber many excellent
Performance, such as excellent resistance to ozone aging, heat-proof aging, weather-resistant, acid and alkali-resistance, remarkable water resistance and excellent electric insulation
Performance etc..The NR of hydrogenation had not only shown the characteristic of EPDM but also had maintained the excellent properties of NR, was a kind of novel green rubber.
The research of the current hydrogenation to NR, is concentrated mainly on reaction mechanism and kinetics；Its HNR hydrogenation degree for preparing
Up to 48%.It is difficult to be obtained the HNR of higher hydrogen degree.
The content of the invention
Goal of the invention of the invention is the HNR for solving the problems, such as to be difficult to that hydrogenation degree high is obtained in the prior art, there is provided one
The method that emulsion method prepares hydrogenation natural gum is planted, the 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 somebody with somebody for catalyst system and catalyzing
Than control hydrogenation degree, although be that H is added dropwise in course of reaction2O2Into 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；From (3), in hydrogenation process, HO free radicals can be while on attack C atoms
Active H atom, crosslinks 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 is adopted the following technical scheme that：
A kind of method that emulsion method prepares hydrogenation natural gum, hydrogenation degree is improved by the way of batch (-type) adds reactant,
Comprise the following steps that：
Heveatex is heated to 45-75 DEG C under agitation, hydrazine hydrate is now added；A certain amount of boric acid is weighed, to go
Added after ion water dissolves；Constant speed is added dropwise appropriate H2O2To reaction system, 1h is reacted in continuation after 7h is dripped off, and stops reaction；Its
C=C double bonds, hydrazine hydrate and H in middle Heveatex NR2O2Mol ratio be 1：1-8：1-10, boric acid addition is 0.1-
0.3mol；Take out reactant to be demulsified with 2% calcium chloride water, HNR rubbers are obtained.
Further, hydrogenated products are washed with deionized, 24h is vacuum dried in 60 DEG C of baking ovens, HNR rubbers are obtained.HNR
Hydrogenation degree is up to 90%.
More specifically technical scheme is：A kind of method that emulsion method prepares hydrogenation natural gum, is added using batch (-type) and reacted
The mode of thing improves hydrogenation degree, comprises the following steps that：
Heveatex is added in toward the four-hole boiling flask with condenser pipe, mechanical agitator and thermometer, mechanical agitation is opened
Oar, heating latex now adds hydrazine hydrate to 55 DEG C；A certain amount of boric acid is accurately weighed, to be added to after deionized water dissolving
In reaction system；Constant speed is added dropwise appropriate H2O2To reaction system, 1h is reacted in continuation after 7h is dripped off, and stops reaction.Take out reaction
Thing is demulsified with 2% calcium chloride water, and hydrogenated products are washed with deionized, and 24h is vacuum dried in 60 DEG C of baking ovens, is obtained
HNR rubbers.C=C in wherein NR:N2H4:H2O2Mol ratio is 1：1-6：1-8, boric acid addition is 0.1M.
Brief description of the drawings
Fig. 1 is that hydrogenation degree of the 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 to determine above-mentioned NR and HNR gel contents curve map respectively using soxhlet extraction methods.
Figure 4 and 5 are that the initial degradation temperature (Tid) of the HNR tested using TGA and most fast degradation temperature (Tmax) are thermally decomposed
Temperature and the glass transition temperature (Tg) by DSC measure HNR.
When Fig. 6 is -25 DEG C, NR and HNR volumes in dilatometer change over time curve.
Specific embodiment
Below in conjunction with the accompanying drawings and specific embodiment, the present invention is expanded on further.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 is to be understood that after the content that the present invention is lectured is read, ability
Field technique personnel can make various changes or modification to the present invention, and these equivalent form of values also belong to the application appended claims
Book limited range.
Raw material used by the present invention：
Heveatex, dry rubber content 60% (mass fraction, similarly hereinafter), the Industrial Co., Ltd. of Shanghai three.
Win dilute your chemical reagent factory reached in hydrazine hydrate, mass fraction 80%, Tianjin.
Hydrogen peroxide, mass fraction 30%, Beijing Chemical Plant.
Boric acid, mass fraction 99.8%, Beijing Yi Li fine chemicals Co., Ltd.
Detecting instrument used by the embodiment of the present invention：
The type NMRs of AV 400 that HNMR Bruker companies of Germany produce analyze the microcosmic knot of NR and HNR samples
Structure；Its hydrogenation degree is calculated by the nmr spectrum of HNR.
The type FTIR of Tensor 27 that FTIR is produced with Bruker companies of Germany carry out infrared attenuation full reflection analysis to HNR,
To study the change of the front and rear strand microstructure of natural rubber hydrogenation.
Thermogravimetric analysis (TGA) is analyzed with the TGA instrument that Mettler Toledo companies produce to HNR rubbers, nitrogen gas
Atmosphere, 10 DEG C/min of heating rate.
Differential scans calorimetric (DSC) HNR is analyzed with the DSC instrument that Mettler Toledo companies produce, nitrogen gas
Atmosphere, 10 DEG C/min of heating rate.
Detection method used of the invention：
Soxhlet extraction methods determine HNR glue gel contents
Sample and m that quality is m are weighed respectively1Filter screen, the filter screen bag equipped with sample is put into extracting barrel, injects toluene,
Sample bag is set to be completely submerged in toluene.Extractor each several part is connected, condensed water current are connected, 24 are stripped in silicone oil bath
Hour, 135 DEG C of silicone oil bath temperature after extracting is finished, takes out filter screen bag, dries, and weigh to obtain m2.Gel content w computing formula are：
W=[(m2-m1)/m] * 100%
Dilatometric method surveys the low temperature crystallization performance of HNR
0.3-0.5gHNR rubbers are cut, its density is surveyed with assay balance method, it is small that sample is vacuumized into heating half at 50 DEG C
When, eliminate thermal history.Sample is fitted into dilatometer, being subsequently added mercury makes the mercury in capillary to certain altitude, remembers
Lower registration.By the temperature setting of high-low temperature test chamber at -25 DEG C, the dilatometer that sample is will be equipped with after stabilization is put into wherein every one
Fix time record registration, calculate Volume Changes.
Embodiment 1：
Heveatex is added in toward the four-hole boiling flask with condenser pipe, mechanical agitator and thermometer, mechanical agitation is opened
Oar, heating latex now adds hydrazine hydrate to 55 DEG C；A certain amount of boric acid is accurately weighed, to be added to after deionized water dissolving
In reaction system；Constant speed is added dropwise appropriate H2O2To reaction system, 1h is reacted in continuation after 7h is dripped off, and stops reaction.C=in NR
C:N2H4:H2O2Mol ratio is 1：1：1, boric acid addition is 0.1M.Take out reactant to be demulsified with 2% calcium chloride water, spend
Ion water washing hydrogenated products, are vacuum dried 24h in 60 DEG C of baking ovens, and prepared hydrogenation degree is：17.6% HNR rubbers.
Embodiment 2：
Heveatex is added in toward the four-hole boiling flask with condenser pipe, mechanical agitator and thermometer, mechanical agitation is opened
Oar, heating latex now adds hydrazine hydrate to 55 DEG C；A certain amount of boric acid is accurately weighed, to be added to after deionized water dissolving
In reaction system；Constant speed is added dropwise appropriate H2O2To reaction system, 1h is reacted in continuation after 7h is dripped off, and stops reaction.C=in NR
C:N2H4:H2O2Mol ratio is 1：2：1.5, boric acid addition is 0.1M.Take out reactant to be demulsified with 2% calcium chloride water, use
Deionized water washs hydrogenated products, and 24h is vacuum dried in 60 DEG C of baking ovens, and prepared hydrogenation degree is 34.6% HNR rubbers.
Embodiment 3：
Heveatex is added in toward the four-hole boiling flask with condenser pipe, mechanical agitator and thermometer, mechanical agitation is opened
Oar, heating latex now adds hydrazine hydrate to 55 DEG C；A certain amount of boric acid is accurately weighed, to be added to after deionized water dissolving
In reaction system；Constant speed is added dropwise appropriate H2O2To reaction system, 1h is reacted in continuation after 7h is dripped off, and stops reaction.C=in NR
C:N2H4:H2O2Mol ratio is 1：3：4.5, boric acid addition is that 0.1M taking-up reactants are demulsified with 2% calcium chloride water, is used
Deionized water washs hydrogenated products, and 24h is vacuum dried in 60 DEG C of baking ovens, and prepared hydrogenation degree is 42.7% HNR rubbers.
Embodiment 4：
Heveatex is added in toward the four-hole boiling flask with condenser pipe, mechanical agitator and thermometer, mechanical agitation is opened
Oar, heating latex now adds hydrazine hydrate to 55 DEG C；A certain amount of boric acid is accurately weighed, to be added to after deionized water dissolving
In reaction system；Constant speed is added dropwise appropriate H2O2To reaction system, 1h is reacted in continuation after 7h is dripped off, and stops reaction.C=in NR
C:N2H4:H2O2Mol 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, 24h is vacuum dried in 60 DEG C of baking ovens, prepared hydrogenation degree is 66.9% HNR rubbers.
Embodiment 5：
Heveatex is added in toward the four-hole boiling flask with condenser pipe, mechanical agitator and thermometer, mechanical agitation is opened
Oar, heating latex now adds hydrazine hydrate to 55 DEG C；A certain amount of boric acid is accurately weighed, to be added to after deionized water dissolving
In reaction system；Constant speed is added dropwise appropriate H2O2To reaction system, 1h is reacted in continuation after 7h is dripped off, and stops reaction.C=in NR
C:N2H4:H2O2Mol ratio is 1：6：8, boric acid addition is 0.2M.Take out reactant to be demulsified with 2% calcium chloride water, spend
Ion water washing hydrogenated products, are vacuum dried 24h in 60 DEG C of baking ovens, and prepared hydrogenation degree is 88.2% HNR rubbers.
Embodiment 6：
Heveatex is added in toward the four-hole boiling flask with condenser pipe, mechanical agitator and thermometer, mechanical agitation is opened
Oar, heating latex now adds hydrazine hydrate to 55 DEG C；A certain amount of boric acid is accurately weighed, to be added to after deionized water dissolving
In reaction system；Constant speed is added dropwise appropriate H2O2To reaction system, 1h is reacted in continuation after 7h is dripped off, and stops reaction.C=in NR
C:N2H4:H2O2Mol ratio is 1：6：10, boric acid addition is 0.2M.Take out reactant to be demulsified with 2% calcium chloride water, use
Deionized water washs hydrogenated products, and 24h is vacuum dried in 60 DEG C of baking ovens, and prepared hydrogenation degree is 89.5% HNR rubbers.
Research finds, during using hydrazine hydrate/hydrogen peroxide/boric acid catalyst system hydrogenation Heveatex, in the presence of boric acid
Under, hydrazine hydrate can be catalyzed carbon-carbon double bond in NR latex with hydrogen peroxide reaction generation hydride presoma imidodicarbonic diamide, imidodicarbonic diamide
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.
Found out by Fig. 1, 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
Diminish 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 be hydrogenation reaction after chemical shift new saturation methyl and methylene H proton peaks is generated 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-1It is alkene=C-H Different Plane rocking vibrations peak to locate；As HNR hydrogenation degrees increase
Greatly, unsaturated C=C double bonds 1663cm-1Absworption peak and 836cm-1The band area of alkene=C-H absworption peaks reduces, 737cm-1(-
CH2-) characteristic absorption peak at place becomes big, illustrates that C=C is unfolded into polyethylene segment.
NR and HNR gel contents are determined respectively using soxhlet extraction methods, as shown in figure 3, with the increase of hydrogenation degree, HNR
Gel content general trend is increase.The NR dry glues not being hydrogenated with contain 13% or so gel in itself, when hydrogenation degree reaches
When 66.9%, gel content is 34.4%.
Initial degradation temperature (the T of the HNR tested using TGAid) and most fast degradation temperature (Tmax) heat decomposition temperature and by
DSC determines the glass transition temperature (Tg) of HNR, such as Fig. 4,5.Be can be seen that with the increase of degree of hydrogenation by Fig. 4 and Biao 1,
The T of HNRidMore and more higher, and NR is above, dotted line represents the T of HNRmaxIn the trend of rising.This absolutely proves that hydrogenation makes shakiness
Fixed C=C keys are converted into more stable C-C keys, the enhancing of strand heat endurance.From the DSC curve of Fig. 5, the Tg of NR for-
65.11 DEG C, with the change of hydrogenation degree, the Tg of HNR slightly has rising, this explanation with the reduction of number of double bonds, molecule it is submissive
Property be decreased slightly as it is low, it is little on the influence of NR resistance to low temperatures.
The glass transition temperature and melt temperature of table 1.HNR samples
| Sample | 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 |
NR meeting occurrence temperature induction crystallizations between -50 DEG C to 10 DEG C, -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 to improve one of the major measure of its lower temperature resistance to reduce crystallization temperature.-25
DEG C when, NR and HNR volumes 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 diminishes, crystallization
Formed；The speed of crystallization is characterized using the time of crystallization generation half, that is, crystallizes half period t1/2, NR and hydrogenation degree are
It is 7h, 140h that 17.6% HNR crystallization half periods are respectively；Hydrogenation degree is that the volume of 34.6% and 42.7% HNR exists respectively
Start slowly to diminish after about 33h and 167h, show that crystallization starts, but up to 500 hours curves are not also gentle, illustrate crystallization not
Up to stabilization.And the volume of 66.9%HNR did not almost change in 500 hours, its almost non-occurrence temperature induction knot is illustrated
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 is probably unordered, uneven so that original regular molecular chain is disturbed, formation after hydrogenation
Part second propylene structure and remaining unsaturated isoprene unit random distribution have influence on the regularity of NR, HNR crystallizing powers
Reduce.
Using hydrazine hydrate/hydrogen peroxide/boric acid system and its consumption is adjusted, highest can prepare 89.5% hydrogenation in NR latex
The HNR of degree.HNR gel contents increasing with hydrogenation degree and increasing, and heat endurance is improved；Glass transition temperature Tg increases with hydrogenation degree
It is big slightly to raise, illustrate that hydrogenation 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
Change the crosslink density of glue as the increase of hydrogenation degree increases.
Claims (5)
1. a kind of method that emulsion method prepares hydrogenation natural gum, hydrogenation degree is improved by the way of batch (-type) adds reactant, is had
Body step is as follows：Heveatex is heated to 45-75 DEG C under agitation, hydrazine hydrate is now added；A certain amount of boric acid is weighed, with
Added after deionized water dissolving；Constant speed is added dropwise appropriate H2O2To reaction system, 1h is reacted in continuation after 7h is dripped off, and stops reaction；
C=C double bonds, hydrazine hydrate and H in wherein Heveatex NR2O2Mol ratio be 1：1-8：1-10, boric acid addition is 0.1-
0.3mol；Take out reactant to be demulsified with 2% calcium chloride water, HNR rubbers are obtained.
2. method according to claim 1, it is characterised in that：Also include being washed with deionized water in prepared HNR rubber steps
Hydrogenated products are washed, 24h is vacuum dried in 60 DEG C of baking ovens.
3. method according to claim 1, it is characterised in that：HNR hydrogenation degrees are up to 90%.
4. claim 1-3 method prepare HNR low temperature crystallization performance test methods, it is characterised in that：Cut 0.3-
0.5gHNR rubbers, its density is surveyed with assay balance method, and sample is vacuumized into heating half an hour at 50 DEG C, thermal history is eliminated, by sample
Product are fitted into dilatometer, and being subsequently added mercury makes the mercury in capillary to certain altitude, registration is write down, by thermocycling
At -25 DEG C, the dilatometer that sample is will be equipped with after stabilization is put into and wherein records registration at regular intervals the temperature setting of case, calculates
Volume Changes.
5. claim 1-3 method prepare HNR gel content method of testing, it is characterised in that：Quality is weighed respectively for m
Sample and m1Filter screen, the filter screen bag equipped with sample is put into extracting barrel, injects toluene, sample bag is completely submerged in toluene,
Extractor each several part is connected, condensed water current are connected, is stripped in silicone oil bath 24 hours, 135 DEG C of silicone oil bath temperature is taken out
Carry after finishing, take out filter screen bag, dry, weigh to obtain m2, gel content w computing formula are：
W=[(m2-m1)/m] * 100%.
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| CN111349184A (en) * | 2018-12-20 | 2020-06-30 | 北京万向新元科技股份有限公司 | Thermo-oxidative aging resistant natural rubber, preparation method thereof and natural rubber product |
| CN113816393A (en) * | 2021-10-19 | 2021-12-21 | 青海利亚达化工有限公司 | Iron removal method for preparing high-purity boric acid |
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| CN111349184A (en) * | 2018-12-20 | 2020-06-30 | 北京万向新元科技股份有限公司 | Thermo-oxidative aging resistant natural rubber, preparation method thereof and natural rubber product |
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| CN113816393A (en) * | 2021-10-19 | 2021-12-21 | 青海利亚达化工有限公司 | Iron removal method for preparing high-purity boric acid |
| 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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