CN107880156A - A kind of epoxidized liquid rubber and preparation method thereof - Google Patents
A kind of epoxidized liquid rubber and preparation method thereof Download PDFInfo
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- CN107880156A CN107880156A CN201711171844.2A CN201711171844A CN107880156A CN 107880156 A CN107880156 A CN 107880156A CN 201711171844 A CN201711171844 A CN 201711171844A CN 107880156 A CN107880156 A CN 107880156A
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- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/04—Oxidation
- C08C19/06—Epoxidation
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Abstract
The present invention relates to a kind of epoxidized liquid rubber and preparation method thereof, it is related to polymeric material field.The preparation method includes：After liquid rubber base material, the solvent for dissolving liquid rubber base material, formic acid, storng-acid cation exchange resin are mixed, hydrogen peroxide is slowly added to, storng-acid cation exchange resin is removed after polymerisation, stratification, takes glue to wash to neutrality, dried after desolvation, technique is simple, and epoxidation efficiency is adjustable, and formic acid dosage is few, and there is relatively low open loop rate, there is preferable commercial application value.The epoxidized liquid rubber as made from the above method have the characteristics that excellent air-tightness, excellent oil resistivity and with the preferable compatibility of other high polymers.
Description
Technical field
The present invention relates to polymeric material field, and more particularly to a kind of epoxidized liquid rubber and preparation method thereof.
Background technology
Liquid rubber is a kind of elastomeric material flowable at room temperature, has good fluidity, simple processing, it is easy to accomplish
Serialization, production efficiency can be improved, the advantages that reducing power consumption, agent can be filled with direct loading and reinforcing agent prepares rubber system
Product, it can also be added in thermosetting resin and other polymer and be modified.Because it has the advantages of incomparable, therefore closely
Several annual consumptions substantially increase.Epoxidation modification is carried out to liquid rubber, can further improve its performance, and it can be widened
Application.Liquid rubber after epoxidation has：It is excellent air-tightness, excellent oil resistivity, preferable with other high polymers
The features such as compatibility.
On the epoxidation of rubber, existing patent CN105801725A prepares ring using dioxane class epoxidation reagent
The method of isoprene rubber is aoxidized, it is necessary to precast epoxidation reagent in advance, technique is more complicated.Publication No. is CN104292372's
Patent proposes two methods to prepare epoxidation trans Isosorbide-5-Nitrae-polydiene compounded rubber, and one kind is to use peracetic acid soln
Method, epoxidation efficiency are low；Another is to use aqueous suspension polymerization, and this method may be only available for solid rubber and not apply to
In liquid rubber.
The content of the invention
It is an object of the invention to provide a kind of epoxidized liquid rubber, it is made, is had excellent airtight by the above method
The features such as property, excellent oil resistivity and compatibility preferable with other high polymers.
Another object of the present invention is to provide a kind of its preparation method of epoxidized liquid rubber, technique is simple, epoxy
It is adjustable to change efficiency, and there is relatively low open loop rate, there is preferable commercial application value.
The present invention is solved its technical problem and realized using following technical scheme.
The present invention proposes a kind of preparation method of epoxidized liquid rubber, and it includes：
Liquid rubber base material, the solvent for dissolving liquid rubber base material, formic acid, storng-acid cation exchange resin are mixed
After conjunction, hydrogen peroxide is slowly added to, storng-acid cation exchange resin is removed after polymerisation, stratification, takes glue to wash
Wash to neutrality, dried after separating solvent.
The present invention proposes that epoxidized liquid rubber made from method is prepared as above in one kind.
The beneficial effect of the epoxidized liquid rubber of the embodiment of the present invention and preparation method thereof is：
Using hydrogen peroxide-formic acid-storng-acid cation exchange resin system, liquid rubber is made by peroxyformic acid in-situ method
Epoxidation reaction occurs for gum base materials.
Wherein, formic acid can keep higher epoxy rate, and still, in epoxidization reaction process, formic acid acidity is stronger, easily with
Ring-opening reaction occurs for epoxy radicals, causes epoxidation poor-performing, influences the performance of final epoxidized liquid rubber.The present invention
In, using storng-acid cation exchange resin as catalyst, after can reducing epoxidation reaction, the formic acid of residual causes formic acid sour
Property too strong, the open loop side reaction being easily caused, effectively improve epoxy rate, and then improve the performance of epoxidized liquid rubber, simultaneously
Effectively reduce the dosage of formic acid.
The epoxidized liquid rubber as made from above-mentioned preparation method, there is the general advantage of epoxidized liquid rubber, such as
Excellent air-tightness, excellent oil resistivity and the preferable compatibility of other high polymers etc..
Brief description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below by embodiment it is required use it is attached
Figure is briefly described, it will be appreciated that the following drawings illustrate only certain embodiments of the present invention, therefore be not construed as pair
The restriction of scope, for those of ordinary skill in the art, on the premise of not paying creative work, can also be according to this
A little accompanying drawings obtain other related accompanying drawings.
Fig. 1 is epoxidized liquid isoprene rubber and unepoxidized liquid isoamyl two prepared by the embodiment of the present invention 5
The infrared contrast spectrogram of alkene rubber.
Fig. 2 is that wave number is 837cm in Fig. 1-1Infrared change spectrogram before and after Isosorbide-5-Nitrae corresponding to place-structure epoxidation.
Embodiment
, below will be in the embodiment of the present invention to make the purpose, technical scheme and advantage of the embodiment of the present invention clearer
Technical scheme be clearly and completely described.Unreceipted actual conditions person, builds according to normal condition or manufacturer in embodiment
The condition of view is carried out.Agents useful for same or the unreceipted production firm person of instrument, it is the conventional production that can be obtained by commercially available purchase
Product.
Epoxidized liquid rubber of the embodiment of the present invention and preparation method thereof is specifically described below.
Epoxidized liquid rubber provided by the invention uses hydrogen peroxide-formic acid-storng-acid cation exchange resin system
Through obtained by epoxidation reaction, belonging to peroxyformic acid in-situ method.
Specifically, the preparation method of epoxidized liquid rubber provided by the invention, including：
Mixed by liquid rubber base material, for the solvent, formic acid, storng-acid cation exchange resin of liquid rubber base material
Afterwards, hydrogen peroxide is slowly added to, storng-acid cation exchange resin is removed after polymerisation, stratification, takes glue to wash
To neutrality, dried after separating solvent.This method technique is simple, and epoxidation efficiency is adjustable, and has relatively low open loop rate, has simultaneously
Effect saves the dosage of formic acid, has preferable commercial application value.
Wherein, higher epoxy rate can be kept using formic acid, still, in epoxidization reaction process, formic acid acidity is stronger,
Ring-opening reaction easily occurs with epoxy radicals, causes epoxidation poor-performing, influences the performance of final epoxidized liquid rubber.This hair
In bright, using storng-acid cation exchange resin as catalyst, after can reducing epoxidation reaction, the formic acid of residual causes formic acid
Acid too strong, the open loop side reaction being easily caused, and then the performance of epoxidized liquid rubber is improved, while effectively reduce the use of formic acid
Amount.
Wherein, in preferred embodiments of the present invention, liquid rubber base material is selected from liquid polybutadiene rubber, liquid isoamyl two
At least one of alkene rubber, liquid styrene butadiene rubber and LNBR, preferred liquid rubber substrate are selected from liquid polybutadiene
Any one of rubber, liquid isoprene rubber, liquid styrene butadiene rubber and LNBR.Using aforesaid liquid rubber-based
The high yield rate that material passes through epoxidized liquid rubber made from the above method.
Preferably, number-average molecular weight≤50000 of liquid rubber base material.
Because liquid rubber is in epoxidation process, the epoxidation activity of Isosorbide-5-Nitrae-double bond is higher than 1,2- double bonds, therefore, Isosorbide-5-Nitrae-
The epoxidation reaction of double bond is very fast compared to the epoxidation reaction of 1,2- double bonds, and epoxide group divides in liquid rubber strand
Cloth is than more uniform.
Therefore, in preferred embodiments of the present invention, liquid rubber base material is the liquid that number-average molecular weight is 30000 or 50000
Body isoprene rubber, it is 91% along Isosorbide-5-Nitrae-structural content in liquid isoprene rubber, 3,4- structural contents are 9%.
Preferably, liquid rubber base material is the liquid polybutadiene rubber of number-average molecular weight 4000 or 8000；The poly- fourth of liquid
It is 78% along Isosorbide-5-Nitrae-structural content in diene rubber, 1,2- structural content is 2%.
Preferably, liquid rubber base material is the liquid styrene butadiene rubber that number-average molecular weight is 4500；In liquid styrene butadiene rubber
The mass ratio of styrene and butadiene is 2/8.
Preferably, liquid rubber base material is the LNBR that number-average molecular weight is 2300, fourth in LNBR
The mass ratio of diene and acrylonitrile is 7/3.
Under above-mentioned condition, epoxidation reaction efficiency is good.
The content of formic acid has a great influence for epoxidised open loop rate, therefore, in preferred embodiments of the present invention, formic acid with
The mol ratio of the double bond of liquid rubber base material is 0.2-1.0：1, preferred molar ratio 0.2-0.45：1.Under the conditions of this ratio,
While with preferable epoxy rate, open loop rate is effectively reduced.
In preferred embodiments of the present invention, hydrogen peroxide and the mol ratio of the double bond of liquid rubber base material are 0.1-0.6：1,
Preferred molar ratio is 0.1-0.3：1.Under the conditions of the ratio, hydrogen peroxide coordinates with formic acid, effectively facilitates the generation of peroxyformic acid,
Promote the probability of double bond epoxidation, while dilute formic acid, suppress open loop rate.
In preferred embodiments of the present invention, the addition of storng-acid cation exchange resin and the addition of liquid rubber base material
The mass ratio of amount is 0.2-0.6：1, such as 0.3：1、0.4：1 or 0.5：1 etc..Under the conditions of the ratio, it can effectively suppress formic acid
Ring-opening reaction.
By adjusting between above-mentioned formic acid, storng-acid cation exchange resin, hydrogen peroxide and liquid rubber base material
Ratio, while effectively reducing open loop rate, obtain required epoxy rate.
In preferred embodiments of the present invention, hydrogen peroxide is the aqueous hydrogen peroxide solution that mass fraction is 88%.
In preferred embodiments of the present invention, formic acid is the formic acid that mass fraction is 30%.
In preferred embodiments of the present invention, storng-acid cation exchange resin is 732 storng-acid cation exchange resins.
In preferred embodiments of the present invention, solvent is selected from least one of chloroform, dimethylbenzene, toluene and ether, wherein,
Solute effect is chloroform ＞ dimethylbenzene ＞ toluene ＞ ether, but because chloroform is expensive and toxicity is larger, it is preferred that molten
Agent is dimethylbenzene.
Polymerization temperature and polymerization time can influence the efficiency and ring opening probability of epoxidation reaction, and temperature is too high to be also easy to cause
Cross-linking reaction, therefore, in preferred embodiments of the present invention, at 20-60 DEG C, hydrogen peroxide is slowly added to, for example with dropwise addition
After mode adds hydrogen peroxide, such as after adding hydrogen peroxide in a manner of dropwise addition in 20-30min, insulation 1-5h is gathered
Close reaction；More preferably, at 30 DEG C, insulation 3h carries out polymerisation, effectively reduces ring opening probability and cross-linking reaction, improves epoxy
Change the efficiency of reaction.
Alternatively, in order to further improve the efficiency of mixing, by liquid rubber base material first after solvent dissolves, then with first
Acid, storng-acid cation exchange resin mixing.
Preferably, the concentration of the liquid rubber base material after dissolving is 0.08-0.17g/ml.
Washing includes wash glue to neutrality with sodium carbonate liquor, after be washed with deionized, such as deionized water is washed
Repeatedly.
Washed by two steps of sodium carbonate liquor, deionized water, fully remove formic acid unnecessary in reaction, while use carbon
Sour sodium, it is easy to remove after reaction, while free from admixture residues in glue.It should be noted that herein repeatedly refer to twice and more than,
Clean result is good.
In the present invention, it is the air drying in vacuum drying chamber preferably to dry.
The epoxidized liquid rubber as made from the above method, have excellent air-tightness, excellent oil resistivity and and its
The features such as its high polymer preferable compatibility.
The feature and performance of the present invention are described in further detail with reference to embodiments.
It should be noted that in embodiment 1-5 provided by the invention, hydrogen peroxide is the peroxidating that mass fraction is 88%
Aqueous solution of hydrogen；Formic acid is the aqueous formic acid that mass fraction is 30%.
Embodiment 1
A kind of epoxidized liquid rubber, it is made by following methods：
By 250mL four-hole bottles clean drying, add number-average molecular weight be 4000 liquid polybutadiene rubber 12.5g,
110ml toluene, 4.0ml formic acid, 5g 732 storng-acid cation exchange resins are well mixed and be warming up to 30 DEG C,
In 20min, hydrogen peroxide 28.2ml is added dropwise under stirring, insulation 5h carries out polymerisation.Reaction is filtered to remove after terminating
Ion exchange resin, stratification, take glue.Glue is washed up to neutrality with sodium carbonate liquor, then number is washed with deionized
It is secondary, after removing solvent toluene with thin film evaporator, the air drying in vacuum drying chamber, produce.
Wherein, the mol ratio of formic acid and the double bond of liquid rubber base material is 0.2：1, hydrogen peroxide and liquid rubber base material
The mol ratio of double bond is 0.6：1.It is 78% along Isosorbide-5-Nitrae-structural content in liquid polybutadiene rubber, 1,2- structural content is
2%.
Its epoxide group molar content is calculated as 55.2% through nuclear-magnetism method.
Embodiment 2
A kind of epoxidized liquid rubber, it is made by following methods：
By 250mL four-hole bottles clean drying, add number-average molecular weight be 30000 liquid polyisoprene rubber 15.7g,
87ml chloroform, 8.01ml formic acid, 6.28g 732 storng-acid cation exchange resins are well mixed and be warming up to 30 DEG C,
In 20min, hydrogen peroxide 28.2ml is added dropwise under stirring, insulation 5h carries out polymerisation.Reaction is crossed after terminating and filtered out
Deionization exchanger resin, stratification.Glue is washed up to neutrality with sodium carbonate liquor, then is washed with deionized for several times, is used
After thin film evaporator desolvation chloroform, the air drying in vacuum drying chamber, produce.
Wherein, the mol ratio of formic acid and the double bond of liquid rubber base material is 0.4：1, hydrogen peroxide and liquid rubber base material
The mol ratio of double bond is 0.6：1.It is 91% along Isosorbide-5-Nitrae-structural content in liquid isoprene rubber, 3,4- structural contents are 9%.
Its epoxy group molar content is calculated as 38.1% through nuclear-magnetism method.
Embodiment 3
A kind of epoxidized liquid rubber, it is made by following methods：
250mL four-hole bottles are cleaned into drying, add liquid styrene butadiene rubber 15.6g, 130ml that number-average molecular weight is 4500
The formic acid of dimethylbenzene, 12.0ml, 6.28g 732 type strong cation-exchanging resins, it is well mixed and is warming up to 50 DEG C, in 20min
It is interior, hydrogen peroxide 14.1ml is added dropwise under stirring, insulation 5h carries out polymerisation.Reaction is filtered to remove ion friendship after terminating
Resin is changed, stratification, takes glue.Glue is washed up to neutrality with sodium carbonate liquor, then is washed with deionized for several times.With thin
After film evaporator removes solvent xylene, the air drying in vacuum drying chamber, produce.
Wherein, the mol ratio of formic acid and the double bond of liquid rubber base material is 0.6：1, hydrogen peroxide and liquid rubber base material
The mol ratio of double bond is 0.3：1.The mass ratio of styrene and butadiene in liquid styrene butadiene rubber is 2/8.
Its epoxy group molar content is calculated as 36.4% through nuclear-magnetism method.
Embodiment 4
A kind of epoxidized liquid rubber, it is made by following methods：
250mL four-hole bottles are cleaned into drying, add LNBR 17.9g, 154ml that number-average molecular weight is 2300
The formic acid of ether, 8.01ml, 7.14g 732 type strong cation-exchanging resins are well mixed and be warming up to 30 DEG C.In 20min
It is interior, hydrogen peroxide 10.8ml is added dropwise under stirring, reacts 5h at a constant temperature.Reaction is filtered to remove amberlite after terminating
Fat, stratification, take glue.Glue is washed up to neutrality with sodium carbonate liquor, then is washed with deionized for several times.Steamed with film
After sending out device removing solvent ether, the air drying in vacuum drying chamber, produce.
Wherein, the mol ratio of formic acid and the double bond of liquid rubber base material is 0.4：1, hydrogen peroxide and liquid rubber base material
The mol ratio of double bond is 0.23：1.The mass ratio of butadiene and acrylonitrile is 7/3 in LNBR.
Its epoxide group molar content is calculated as 40.3% through nuclear-magnetism method.
Embodiment 5
A kind of epoxidized liquid rubber, it is made by following methods：
250mL four-hole bottles are cleaned into drying, add the poly- isoamyl two of liquid that the homemade number-average molecular weight in laboratory is 30000
Alkene rubber 15.7g, 130ml dimethylbenzene, 8.0ml formic acid, 6.28g 732 type strong cation-exchanging resins, it is well mixed simultaneously
It is warming up to 35 DEG C.In 20min, hydrogen peroxide 7.07ml is added dropwise under stirring, reacts 3h at a constant temperature.After reaction terminates
Ion exchange resin is filtered to remove, stratification, takes glue.Glue is washed up to neutrality with sodium carbonate liquor, then uses deionization
Water washing is for several times.After removing solvent xylene with thin film evaporator, the air drying in vacuum drying chamber, produce.
Wherein, the mol ratio of formic acid and the double bond of liquid rubber base material is 0.4：1, hydrogen peroxide and liquid rubber base material
The mol ratio of double bond is 0.15：1.It is 91% along Isosorbide-5-Nitrae-structural content in liquid isoprene rubber, 3,4- structural contents are 9%.
Its epoxy group molar content is calculated as 40.6% through nuclear-magnetism method.
Test example
Determine the epoxidized liquid rubber after liquid rubber base material and its polymerisation respectively using infrared spectrometer
Spectrogram, according to the change of spectrogram at double bond before and after epoxidation reaction, judge whether that epoxidation reaction occurs.
It should be noted that in the present invention, the test for epoxy content is determined using nucleus magnetic hydrogen spectrum figure instrument.It tests formula
It is as follows：Assuming that the molar content a% of epoxide group, its calculation formula are：A%=[2.17I/ (2.17I+5.11I)] * 100%,
Wherein, 2.17I represents the peak area at 2.17, and 5.11I represents the peak area at 5.11.
Fig. 1 is that embodiment 5 carries out epoxidation using liquid isoprene rubber, and the epoxidation that the epoxy content of preparation is 40.6% is different
The infrared contrast spectrogram of pentadiene rubber and unepoxidized liquid isoprene rubber.
Fig. 2 is that wave number is 837cm in Fig. 1-1Infrared change spectrogram before and after Isosorbide-5-Nitrae corresponding to place-structure epoxidation.According to figure
2, it can be seen that wave number 837cm-1Locate, the spectrogram before and after epoxidation reaction at double bond substantially changes, therefore, it is determined that liquid
There occurs epoxidation reaction for isoprene rubber.
To sum up, its preparation method of the epoxidized liquid rubber of the offer of the embodiment of the present invention, technique is simple, epoxidation effect
Rate is adjustable, and has relatively low open loop rate, has preferable commercial application value.Obtained epoxidized liquid rubber has excellent
Air-tightness, excellent oil resistivity and the features such as compatibility preferable with other high polymers.
Embodiments described above is part of the embodiment of the present invention, rather than whole embodiments.The reality of the present invention
The detailed description for applying example is not intended to limit the scope of claimed invention, but is merely representative of the selected implementation of the present invention
Example.Based on the embodiment in the present invention, what those of ordinary skill in the art were obtained under the premise of creative work is not made
Every other embodiment, belongs to the scope of protection of the invention.
Claims (10)
- A kind of 1. preparation method of epoxidized liquid rubber, it is characterised in that including：Liquid rubber base material, the solvent for dissolving liquid rubber base material, formic acid, storng-acid cation exchange resin are mixed Afterwards, hydrogen peroxide is slowly added to, the storng-acid cation exchange resin is removed after polymerisation, stratification, takes glue Washing is dried to neutrality after separating the solvent.
- 2. preparation method according to claim 1, it is characterised in that the double bond of the formic acid and the liquid rubber base material Mol ratio be 0.2-1.0：1, preferred molar ratio 0.2-0.45：1；Preferably, the hydrogen peroxide and the mol ratio of the double bond of the liquid rubber base material are 0.1-0.6：1, preferred molar ratio For 0.1-0.3：1.
- 3. preparation method according to claim 1, it is characterised in that the addition of the storng-acid cation exchange resin Mass ratio with the addition of the liquid rubber base material is 0.2-0.6：1；Preferably, the storng-acid cation exchange resin is 732 storng-acid cation exchange resins.
- 4. preparation method according to claim 1, it is characterised in that the liquid rubber base material is selected from liquid polybutadiene At least one of rubber, liquid isoprene rubber, liquid styrene butadiene rubber and LNBR；Preferably, number-average molecular weight≤50000 of the liquid rubber base material.
- 5. preparation method according to claim 1, it is characterised in that the liquid rubber base material is that number-average molecular weight is 30000 or 50000 liquid isoprene rubber, it is 91% along Isosorbide-5-Nitrae-structural content, 3,4- structures contain in the liquid isoprene rubber Measure as 9%；Preferably, the liquid rubber base material is the liquid polybutadiene rubber of number-average molecular weight 4000 or 8000；The liquid It is 78% along Isosorbide-5-Nitrae-structural content in polybutadiene rubber, 1,2- structural content is 2%；Preferably, the liquid rubber base material is the liquid styrene butadiene rubber that number-average molecular weight is 4500；The liquid styrene butadiene rubber In styrene and butadiene mass ratio be 2/8；Preferably, the liquid rubber base material is the LNBR that number-average molecular weight is 2300, the LNBR The mass ratio of middle butadiene and acrylonitrile is 7/3.
- 6. preparation method according to claim 1, it is characterised in that the solvent is selected from chloroform, dimethylbenzene, toluene and second At least one of ether, preferably dimethylbenzene.
- 7. preparation method according to claim 1, it is characterised in that at 20-60 DEG C, after being slowly added to hydrogen peroxide, protect Warm 1-5h carries out polymerisation；Preferably, at 30 DEG C, insulation 3h carries out polymerisation.
- 8. preparation method according to claim 1, it is characterised in that the liquid rubber base material is first molten through the solvent Xie Hou, then mixed with the formic acid, the storng-acid cation exchange resin；Preferably, the concentration of the liquid rubber base material after dissolving is 0.08-0.17g/ml.
- 9. preparation method according to claim 1, it is characterised in that washing includes：The glue is washed with sodium carbonate liquor Liquid to neutrality, after be washed with deionized again.
- 10. epoxidized liquid rubber made from the preparation method as described in claim 1-9 any one.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111647102A (en) * | 2020-05-29 | 2020-09-11 | 西安航天三沃化学有限公司 | Epoxidized hydroxyl-terminated polybutadiene and preparation method thereof |
| CN112250776A (en) * | 2020-08-13 | 2021-01-22 | 沧州信联化工有限公司 | Tetramethyl ammonium hydroxide catalytic thermoplastic material and preparation method thereof |
| CN114349910A (en) * | 2022-03-03 | 2022-04-15 | 河北科技大学 | Epoxidized styrene-butadiene latex and preparation method and application thereof |
| CN115418188A (en) * | 2022-09-30 | 2022-12-02 | 深圳市优宝新材料科技有限公司 | Composite modified epoxy resin adhesive and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111647102A (en) * | 2020-05-29 | 2020-09-11 | 西安航天三沃化学有限公司 | Epoxidized hydroxyl-terminated polybutadiene and preparation method thereof |
| CN112250776A (en) * | 2020-08-13 | 2021-01-22 | 沧州信联化工有限公司 | Tetramethyl ammonium hydroxide catalytic thermoplastic material and preparation method thereof |
| CN112250776B (en) * | 2020-08-13 | 2022-07-22 | 沧州信联化工有限公司 | Tetramethyl ammonium hydroxide catalytic thermoplastic material and preparation method thereof |
| CN114349910A (en) * | 2022-03-03 | 2022-04-15 | 河北科技大学 | Epoxidized styrene-butadiene latex and preparation method and application thereof |
| CN114349910B (en) * | 2022-03-03 | 2024-01-09 | 河北科技大学 | Epoxidized styrene-butadiene latex and preparation method and application thereof |
| CN115418188A (en) * | 2022-09-30 | 2022-12-02 | 深圳市优宝新材料科技有限公司 | Composite modified epoxy resin adhesive and preparation method thereof |
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Application publication date: 20180406 |