CN102086363A - Epoxy resin adhesive using modified multielement sulfur alcohol as solidifying agent and preparation method thereof - Google Patents
Epoxy resin adhesive using modified multielement sulfur alcohol as solidifying agent and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an epoxy resin adhesive, in particular to an epoxy resin adhesive using modified multielement sulfur alcohol as a solidifying agent and a preparation method thereof. The epoxy resin adhesive comprises the following raw materials: a component A and a component B, wherein the component A comprises the following components in parts by weight: 100 parts of epoxy resins E-44, 100-350 parts of talcum powder and 10-100 parts of gaseous-phase white carbon black; and the component B comprises the following components of: 10-80 parts of modified multielement sulfur alcohol, 100-350 parts of talcum powder and 10-100 parts of gaseous-phase white carbon black. The multielement sulfur alcohol is prepared from multielement alcohol by multi-step reaction and then reacts with multielement isocyanate to prepare the modified multielement sulfur alcohol so that the epoxy resin adhesive has the characteristics of rapidness for solidification at low temperature and normal temperature, high reaction activity, small smell, no toxicity, good storage stability and the like. The prepared modified multielement sulfur alcohol is used as a solidifying agent and forms the adhesive with the epoxy resins and other components, after being solidified within 1.5h at low temperature and within 1h at room temperature, the solidified epoxy resin adhesive has excellent physical and chemical properties, such as flexibility and the like, and the epoxy resin adhesive is suitable for the rapid repairing and adhesion of metals and the using field of epoxy resins.
Description
Technical field
The present invention relates to a kind of epoxyn, especially relating to a kind of is the epoxyn and preparation method thereof of solidifying agent with modified multicomponent mercaptan.
Background technology
Resins, epoxy is the thermosetting polymer synthetic materials that a class has performances such as good bonding, corrosion-resistant, electric insulation, high strength.It has been widely used in the manufacturing of multiple metal and nonmetallic bonding, corrosion resistant coating, insulating material, glass reinforced plastic/matrix material etc.It plays important effect in electronics, electric, machinofacture, chemical anticorrosion, aerospace, ship and other many industrial circles, become indispensable base mateiral in each industrial circle.
In Resins, epoxy was used, solidifying agent occupied crucial status, and epoxy curing agent is various in style, the current room temperature solidifying agent generally uses aliphatic polyamine class solidifying agent, its toxicity is bigger, and is strong to the human body skin pungency, big with Resins, epoxy exothermic heat of reaction amount, the cured article snappiness is poor.The most tangible deficiency is that curing speed is too slow under the low temperature, even also need 24h under 25 ℃ normal temperature, can't require quick-setting occasion to use under low temperature or normal temperature.And sulfur alcohol compound can be under-20 ℃ low temperature fast-curing epoxy resin, it is being repaired and the winter job occasion has great advantage fast, for the other types solidifying agent can't substitute.Produce thiol-cured dose of useful thiohydracrylic acid esterification method [Kang F.C at present, Zhang H.W, ThermosettingResin, 2006,21 (3): 15-19], but cost is higher, and also useful Sodium sulfhydrate is introduced sulfydryl method [Wang A.T, ThermosettingResin, 2009,24 (1): 17-19], its toxicity is big, operation inconvenience.Also have bibliographical information [Cui Z, Lu C, Yang B, ShenJ, Su X, Yang H, Polymer, 2001,42 (26): 10095-10100], mercaptan is equipped with a small amount of tertiary amine and promptly can be used as the solidifying agent use.But all there is little, the easy shortcoming of big, the Resins, epoxy snappiness difference after solidifying of oxidized, smell of molecular weight in these small molecules mercaptan.Preparation can be under low temperature and normal temperature fast setting, cured product has good snappiness again simultaneously, is the difficult problem of epoxy resin cure research always.As everyone knows, because cross-linking density and pattern after solidifying agent decision cured resin is crosslinked, therefore the structure of solidifying agent is to the required gel time of cured epoxy resin and to solidify the influence of physical and chemical performance of back resin great, the structure that changes solidifying agent can improve the intensity of solidifying the back resin, over-all propertieies such as hardness and snappiness to a great extent.
Summary of the invention
It is the epoxyn and preparation method thereof of solidifying agent with modified multicomponent mercaptan that the present invention aims to provide a kind of.
Of the present invention is that the raw material of the epoxyn of solidifying agent is formed and as follows by the content of mass ratio with modified multicomponent mercaptan:
A component: E-44 Resins, epoxy 100, talcum powder 100～350 and gas-phase silica 10～100;
B component: modified multicomponent mercaptan 10～80, talcum powder 100～350 and gas-phase silica 10～100.
Described modified multicomponent mercaptan is the high molecular multi-thiol product of multi-thiol and polyisocyanates reaction gained.
Of the present invention is that the preparation method of the epoxyn of solidifying agent may further comprise the steps with modified multicomponent mercaptan:
1) prepares polynary hydrobromic ether by polyvalent alcohol
In container, be 1 in molar ratio: n (n is the number of hydroxyl in the polyvalent alcohol molecule) adds polyvalent alcohol and Sodium Bromide, adds sulfuric acid, heated and stirred changes reaction solution in the separating funnel over to after refluxing, and tells organic phase, get extraction liquid with the extracted with diethyl ether water, be washed till neutrality with saturated sodium carbonate solution and distilled water successively, drying is filtered, remove ether, through underpressure distillation, collect cut again, get polynary hydrobromic ether;
In step 1), described adding sulfuric acid is preferably in the ice-water bath cooling and adds sulfuric acid down; The time that described heated and stirred refluxes can be 4～5h; Behind the described extracted with diethyl ether water of using, available extracted with diethyl ether water 3 times, combining extraction liquid; Described drying can adopt the Calcium Chloride Powder Anhydrous drying; In this reaction, hydroxyl groups is replaced by bromine;
The preparation feedback formula (is example with a condensed ethandiol) that is prepared polynary hydrobromic ether by polyvalent alcohol is as follows:
Described polyvalent alcohol can be a condensed ethandiol, ethylene glycol, 1,2-propylene glycol, 1,4-butyleneglycol, 1,6-hexylene glycol, neopentyl glycol, dipropylene glycol, trihydroxy-propane, glycerine, 1,2,6-hexylene glycol, methyl propanediol, a kind of in the tetramethylolmethane etc.
2) by polynary hydrobromic ether and thiocarbamide prepared in reaction multi-thiol
Addition: thiocarbamide is added in the ethanol, and heated and stirred drips polynary hydrobromic ether to dissolving fully again by dropping funnel, and exothermic heat of reaction refluxes reaction, and the white solid adduct is separated out in cooling then, and suction filtration, drying obtain adduct;
Cracking: adduct after the reaction, obtains organosulfur sodium alkoxide mixing solutions through the NaOH heating pyrolyze;
Neutralization: with sulfuric acid under ice bath and organosulfur sodium alkoxide mixing solutions carry out neutralization reaction, get the upper strata and get the polythiol product, acid layer is with ether extraction at least 1 time, washing ether layer, the Calcium Chloride Powder Anhydrous drying, the merging product gets the multi-thiol ether solution.
Refining and distilling: ether solution distills under water-bath, with water pump bleed ether and the single mercaptan of decompression Ex-all remnants, gets multi-thiol with the oil pump underpressure distillation again when closely dried;
In step 2) in, described ethanol can adopt concentration 95% ethanol; The temperature of described heated and stirred can be 60～70 ℃; Described adduct can be 1.0～3.0h through the reaction times of NaOH heating pyrolyze;
Preparation feedback formula (is example with dibromo one condensed ethandiol) by polynary hydrobromic ether and thiocarbamide prepared in reaction multi-thiol is as follows:
3) multi-thiol prepares modified multicomponent mercaptan
Multi-thiol, polyisocyanates are put into container, and logical nitrogen stirs, and add CaCl on prolong
2Drying tube, reflux stirs then, gets modified multicomponent mercaptan product;
In step 3), the temperature that described reflux stirs can be 50 ℃, and the time that reflux stirs can be 10h.
The preparation feedback formula (is example with dimercapto one condensed ethandiol and hexamethylene diisocyanate (HDI) reaction) that is prepared modified multicomponent mercaptan by multi-thiol is as follows:
Wherein, R=-CH
2CH
2CH
2CH
2CH
2CH
2-.
4) preparation is the epoxyn of solidifying agent with modified multicomponent mercaptan
(1) E-44 Resins, epoxy, talcum powder and gas-phase silica are mixed, get compound A component;
(2) modified multicomponent mercaptan, talcum powder and gas-phase silica are mixed, get compound B component, be able to the epoxyn that modified multicomponent mercaptan is solidifying agent.
In step 4) (1) part, described mixing can adopt electric blender to mix, and the rotating speed of electric blender can be 20～100r/min, and the described blended time can be 60～100min.
In step 4) (2) part, described mixing can adopt electric blender to mix, and the rotating speed of electric blender can be 20～100r/min, and the described blended time can be 60～100min.
Under 20 ℃, A component and B component are mixed, bonding steel plate-steel plate, copper coin-copper coin, aluminum strip-aluminum strip, wooden unit-wooden unit, stone bar-stone bar all solidifies within 1h.It is as shown in table 1 to measure its tensile strength.
Table 1
| Steel plate-steel plate | Copper coin-copper coin | Aluminum strip-aluminum strip | Wooden unit-wooden unit | Stone bar-stone bar | |
| Tensile strength/MPa | 20～28 | 18～24 | 23～30 | 12～16 | 17～24 |
The present invention adopts polyvalent alcohol to make multi-thiol through polystep reaction, and the modified multicomponent mercaptan that the reaction of itself and multicomponent isocyanate is made has and solidifies under low temperature and normal temperature rapidly again, the reactive behavior height, and smell is little, nontoxicity, characteristics such as stability in storage is good.Modified multicomponent mercaptan with preparation is worked as solidifying agent, form tackiness agent with Resins, epoxy and other component, low temperature (about 4 ℃) 1.5h with interior and self-vulcanizing time in 1h, physical and chemical performances such as the Resins, epoxy snappiness after the curing are good, be specially adapted to the quick repairing between metal-metal and bonding under low temperature and the room temperature, be applicable to all use fields of Resins, epoxy simultaneously, have very high using value.
Embodiment
Embodiment 1
1) prepares polynary hydrobromic ether by polyvalent alcohol
In the 100ml round-bottomed flask, adding 10.6g one condensed ethandiol and 20.8g Sodium Bromide (mol ratio is 1: 2) shakes up, under the ice-water bath cooling, add the 39.2g vitriol oil then, heated and stirred refluxes behind 4～5h, reaction solution is changed in the separating funnel, tell organic phase, behind extracted with diethyl ether water three times, combining extraction liquid is washed till neutrality with saturated sodium carbonate solution and distilled water successively, use the Calcium Chloride Powder Anhydrous drying, filter, remove ether through Rotary Evaporators, again through underpressure distillation, collect cut, make dibromo one condensed ethandiol.
2) by polynary hydrobromic ether and thiocarbamide prepared in reaction multi-thiol
Addition: get the 11.0g thiocarbamide, 95% ethanol 50ml puts into the three-necked bottle of 150ml, be heated to 70 ℃ and be stirred to dissolving fully, 11.6g dibromo one condensed ethandiol is added dropping funnel drip, exothermic heat of reaction, control rate of addition, about 2h slowly refluxes, naturally cooling is separated out the solid adduct, and suction filtration, drying obtain adduct.
Cracking: with the 10g adduct, 7gNaOH, 100ml distilled water add in the 250ml three-necked bottle, and jolting makes it dissolving, heat release, and reflux 2h obtains xanchromatic two sodium mercaptides one condensed ethandiol product solution.
Neutralization: under ice bath, carry out neutralization reaction fast with 15ml50% sulfuric acid and two sodium mercaptides, one condensed ethandiol, be neutralized to PH=1-2, obtain colorless oil polythiol product, separate with separating funnel, subnatant extracted with diethyl ether 2 times, washing ether layer 1 time, the Calcium Chloride Powder Anhydrous drying merges the diethyl ether solution that product gets dimercapto one condensed ethandiol.
Refining and distilling: the ether solution of dimercapto one condensed ethandiol boils off ether under water-bath, again with ether and the single mercaptan of water pump decompression Ex-all remnants; Obtain the refined products 4g of dimercapto one condensed ethandiol again with the oil pump underpressure distillation.
3) multi-thiol prepares modified multicomponent mercaptan
With 13.8g dimercapto one condensed ethandiol, 10.0g 1,6 diisocyanate based hexane (HDI) is put into the 100ml three-necked bottle, and logical nitrogen stirs, and add CaCl on prolong
2Drying tube stirs 10h 50 ℃ of following reflux then, obtains with isocyanate-modified modified multicomponent mercaptan.
4) preparation of low temperature and normal temperature fast-curing epoxy resin tackiness agent
The preparation of A component
Take by weighing 100g E-44 Resins, epoxy, 300g talcum powder and 50g gas-phase silica, the aforementioned component that takes by weighing is mixed with electric blender, and the rotating speed of electric blender is controlled to be 50r/min, after mixing 90min, obtain compound component A, component A is packed by desired packing specifications.
The preparation of B component
Taking by weighing 50g above-mentioned modification binary mercaptan, talcum powder 200g and 50g gas-phase silica mixes with electric blender, the rotating speed of electric blender is controlled to be 50n/min, after mixing 90min, obtain compound component B, by desired packing specifications component B is packed.
Embodiment 2
As embodiment 1, change 10.6g one condensed ethandiol wherein into the 6.2g ethylene glycol with isocyanate-modified dimercapto ethylene glycol, 11.6g dibromo one condensed ethandiol changes 9.4g dibromo ethylene glycol into, change 13.8g dimercapto one condensed ethandiol into 11.0g dimercapto ethylene glycol, and all change wherein all condensed ethandiols into ethylene glycol.
Embodiment 3
As embodiment 1, change wherein 10.6g one condensed ethandiol into 7.6g one and contract the propylene glycol preparation with isocyanate-modified dimercapto one propylene glycol that contracts, 11.6g dibromo one condensed ethandiol changes 10.1g dibromo one propylene glycol that contracts into, change 13.8g dimercapto one condensed ethandiol into 10.8g dimercapto one propylene glycol that contracts, and will wherein all condensed ethandiols all change the propylene glycol that contracts into.
Embodiment 4
As embodiment 1, change 10.6g one condensed ethandiol wherein into 9.0g1, the preparation of 4-butyleneglycol is with isocyanate-modified dimercapto 1, the 4-butyleneglycol, 11.6g dibromo one condensed ethandiol changes 10.8g dibromo 1 into, the 4-butyleneglycol, change 13.8g dimercapto one condensed ethandiol into 12.2g dimercapto 1, the 4-butyleneglycol, and all change wherein all condensed ethandiols into 1, the 4-butyleneglycol.
Embodiment 5
As embodiment 1, change 10.6g one condensed ethandiol wherein into 11.8g1, the preparation of 6-hexylene glycol is with isocyanate-modified dimercapto 1, the 6-hexylene glycol, 11.6g dibromo one condensed ethandiol changes 12.2g dibromo 1 into, the 6-hexylene glycol, change 13.8g dimercapto one condensed ethandiol into 15.0g dimercapto 1, the 6-hexylene glycol, and all change wherein all condensed ethandiols into 1, the 6-hexylene glycol.
Embodiment 6
As embodiment 1, change 10.6g one condensed ethandiol wherein the preparation of into 10.4g neopentyl glycol with isocyanate-modified dimercapto neopentyl glycol, 11.6g dibromo one condensed ethandiol changes the 11.5g dibromoneopentyl glycol into, change 13.8g dimercapto one condensed ethandiol into 13.6g dimercapto neopentyl glycol, and all change wherein all condensed ethandiols into 1, the 6-hexylene glycol.
Embodiment 7
As embodiment 1, change 10.6g one condensed ethandiol wherein the preparation of into 13.4g dipropylene glycol with isocyanate-modified dimercapto dipropylene glycol, 11.6g dibromo one condensed ethandiol changes 13.0g dibromo dipropylene glycol into, change 13.8g dimercapto one condensed ethandiol into 16.6g dimercapto dipropylene glycol, and all change wherein all condensed ethandiols into dipropylene glycol.
Embodiment 8
As embodiment 1, change 10.6g one condensed ethandiol wherein the preparation of into 6.2g glycerine with isocyanate-modified tri-thiol glycerine, 11.6g tribromo one condensed ethandiol changes 9.3g tribromo glycerine into, change 13.8g dimercapto one condensed ethandiol into 9.3g tri-thiol glycerine, and all change wherein all condensed ethandiols into glycerine.
Embodiment 9
As embodiment 1, change 10.6g one condensed ethandiol wherein the preparation of into 6.8g tetramethylolmethane with four isocyanate-modified sulfydryl tetramethylolmethanes, 11.6g tribromo one condensed ethandiol changes 9.7g tetrabromo tetramethylolmethane into, change 13.8g dimercapto one condensed ethandiol into 10.0g four sulfydryl tetramethylolmethanes, and all change wherein all condensed ethandiols into tetramethylolmethane.
Embodiment 10
As embodiment 1～9, change 16.8g 1,6 diisocyanate based hexane (HDI) into 17.4g tolylene diisocyanate (TDI).
Embodiment 11
As embodiment 1～9, change 16.8g 1,6 diisocyanate based hexane (HDI) into 25.0g4,4 '-diphenylmethanediisocyanate (MDI).
Embodiment 12
As embodiment 1～9, change 16.8g 1,6 diisocyanate based hexane (HDI) into 15.6g poly methylene poly phenyl poly isocyanate (PAPI).
Embodiment 13
As embodiment 1～9, change 16.8g 1,6 diisocyanate based hexane (HDI) into 18.4g isophorone diisocyanate (IPDI).
Embodiment 14
As embodiment 1～9, change 16.8g 1,6 diisocyanate based hexane (HDI) into 18.8g xylylene diisocyanate (XDI).
Embodiment 15
As embodiment 1～9, change 16.8g 1,6 diisocyanate based hexane (HDI) into 21.3g trimethyl hexamethylene diisocyanate (TMDI).
Embodiment 16
As embodiment 1～9, change 16.8g 1,6 diisocyanate based hexane (HDI) into 26.8g dimer acid diisocyanate (DDI).
Embodiment 17
As embodiment 1～9, change 16.8g 1,6 diisocyanate based hexane (HDI) into 15.8g lysinediisocyanate (LDI).
Embodiment 18 diethyl fumarate diisocyanates (FDI)
As embodiment 1～9, change 16.8g 1,6 diisocyanate based hexane (HDI) into 26.2g dicyclohexyl methane diisocyanate (HMDI).
Embodiment 19
As embodiment 1～9, change 16.8g 1,6 diisocyanate based hexane (HDI) into 20.8g 3-methyl cyclohexanol group diisocyanate (HTDI).
Embodiment 20
As embodiment 1～9, change 16.8g 1,6 diisocyanate based hexane (HDI) into 24.4g tetramethylxylylene diisocyanate (TMXDI).
The present invention is with multi-thiol and polyisocyanates reaction, on the one hand, the modified multicomponent thiol molecule amount that obtains improves, in the molecule except can play the fast setting effect-the SH group, also contain a large amount of can play the ambient cure effect-the NH group, improved the crosslinked group density in the solidifying agent effectively, the reactive behavior under low temperature and the normal temperature is obviously improved; And smell reduces, and nontoxicity has been avoided the shortcoming of the easy oxidized generation foul odour of small molecules mercaptan, and stability in storage is good.On the other hand, modification mercaptan is owing to having concurrently easily and the nitrogen-atoms and the sulphur atom of metal generation complexing, and is big with metallic surface reactivity ratio's small molecules mercaptan, is specially adapted to the connection between metal-metal.The most important thing is, the epoxyn made from this novel solidifying agent can be under low temperature and normal temperature fast setting, the Resins, epoxy after the curing has good physical and chemical performance, particularly snappiness good again.
Claims (10)
1. be the epoxyn of solidifying agent with modified multicomponent mercaptan, it is characterized in that its raw material composition and as follows by the content of mass ratio:
A component: E-44 Resins, epoxy 100, talcum powder 100～350 and gas-phase silica 10～100;
B component: modified multicomponent mercaptan 10～80, talcum powder 100～350 and gas-phase silica 10～100.
2. as claimed in claim 1 is the epoxyn of solidifying agent with modified multicomponent mercaptan, it is characterized in that described modified multicomponent mercaptan is the high molecular multi-thiol product of multi-thiol and polyisocyanates reaction gained.
3. as claimed in claim 1 is the preparation method of the epoxyn of solidifying agent with modified multicomponent mercaptan, it is characterized in that may further comprise the steps:
1) prepares polynary hydrobromic ether by polyvalent alcohol
In container, be 1 in molar ratio: n adds polyvalent alcohol and Sodium Bromide, and n is the number of hydroxyl in the polyvalent alcohol molecule, add sulfuric acid, heated and stirred changes reaction solution in the separating funnel over to after refluxing, tell organic phase, get extraction liquid, be washed till neutrality with saturated sodium carbonate solution and distilled water successively with the extracted with diethyl ether water, dry, filter, remove ether, again through underpressure distillation, collect cut, get polynary hydrobromic ether;
2) by polynary hydrobromic ether and thiocarbamide prepared in reaction multi-thiol
Addition: thiocarbamide is added in the ethanol, and heated and stirred drips polynary hydrobromic ether to dissolving fully again by dropping funnel, and exothermic heat of reaction refluxes reaction, and the white solid adduct is separated out in cooling then, and suction filtration, drying obtain adduct;
Cracking: adduct after the reaction, obtains organosulfur sodium alkoxide mixing solutions through the NaOH heating pyrolyze;
Neutralization: with sulfuric acid under ice bath and organosulfur sodium alkoxide mixing solutions carry out neutralization reaction, get the upper strata and get the polythiol product, acid layer is with ether extraction at least 1 time, washing ether layer, the Calcium Chloride Powder Anhydrous drying, the merging product gets the multi-thiol ether solution;
Refining and distilling: ether solution distills under water-bath, with water pump bleed ether and the single mercaptan of decompression Ex-all remnants, gets multi-thiol with the oil pump underpressure distillation again when closely dried;
3) multi-thiol prepares modified multicomponent mercaptan
Multi-thiol, polyisocyanates are put into container, and logical nitrogen stirs, and add CaCl on prolong
2Drying tube, reflux stirs then, gets modified multicomponent mercaptan product;
4) preparation is the epoxyn of solidifying agent with modified multicomponent mercaptan
(1) E-44 Resins, epoxy, talcum powder and gas-phase silica are mixed, get compound A component;
(2) modified multicomponent mercaptan, talcum powder and gas-phase silica are mixed, get compound B component, be able to the epoxyn that modified multicomponent mercaptan is solidifying agent.
4. as claimed in claim 3 is the preparation method of the epoxyn of solidifying agent with modified multicomponent mercaptan, it is characterized in that in step 1), and described adding sulfuric acid is to add sulfuric acid under the ice-water bath cooling; The time that described heated and stirred refluxes is 4～5h.
5. as claimed in claim 3 is the preparation method of the epoxyn of solidifying agent with modified multicomponent mercaptan, it is characterized in that in step 1), and the described extracted with diethyl ether water of using is with behind the extracted with diethyl ether water 3 times, combining extraction liquid; Described drying is to adopt the Calcium Chloride Powder Anhydrous drying.
6. as claimed in claim 3 is the preparation method of the epoxyn of solidifying agent with modified multicomponent mercaptan, it is characterized in that in step 1), and described polyvalent alcohol is a condensed ethandiol, ethylene glycol, 1,2-propylene glycol, 1, the 4-butyleneglycol, 1, the 6-hexylene glycol, neopentyl glycol, dipropylene glycol, trihydroxy-propane, glycerine, 1,2, the 6-hexylene glycol, methyl propanediol, a kind of in the tetramethylolmethane.
7. as claimed in claim 3 is the preparation method of the epoxyn of solidifying agent with modified multicomponent mercaptan, it is characterized in that in step 2) in, described ethanol is to adopt concentration 95% ethanol; The temperature of described heated and stirred is 60～70 ℃; Described adduct is 1.0～3.0h through the reaction times of NaOH heating pyrolyze.
8. as claimed in claim 3 is the preparation method of the epoxyn of solidifying agent with modified multicomponent mercaptan, it is characterized in that in step 3), and the temperature that described reflux stirs is 50 ℃, and the time that reflux stirs is 10h.
9. as claimed in claim 3 is the preparation method of the epoxyn of solidifying agent with modified multicomponent mercaptan, it is characterized in that in step 4) (1) part, described mixing, be to adopt electric blender to mix, the rotating speed of electric blender is 20～100r/min, and the described blended time is 60～100min.
10. as claimed in claim 3 is the preparation method of the epoxyn of solidifying agent with modified multicomponent mercaptan, it is characterized in that in step 4) (2) part, described mixing, be to adopt electric blender to mix, the rotating speed of electric blender is 20～100r/min, and the described blended time is 60～100min.
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| CN105566183A (en) * | 2016-03-21 | 2016-05-11 | 太原理工大学 | Preparation method of 4,4'-dimercaptodiphenylsulfide |
| CN109721474A (en) * | 2017-10-30 | 2019-05-07 | 中国石油天然气股份有限公司 | A kind of synthetic method of dichloroether and 2- chloroethoxyethanol |
| CN110938401A (en) * | 2019-12-13 | 2020-03-31 | 山东益丰生化环保股份有限公司 | Special adhesive for bulletproof material |
| CN111018756A (en) * | 2019-12-13 | 2020-04-17 | 山东益丰生化环保股份有限公司 | Preparation method of 2-2-dimercaptomethyl-1-3-propanedithiol |
| CN116194540A (en) * | 2020-09-22 | 2023-05-30 | Cht德国有限公司 | Formaldehyde-free printing ink for printing on fabrics |
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| CN102516912A (en) * | 2011-11-30 | 2012-06-27 | 安徽中铁工程材料科技有限公司 | Method for preparing composite curing agent modified bisphenol F thermosetting adhesive repairing agent special for ballastless track gap and crack damage |
| CN102516912B (en) * | 2011-11-30 | 2013-09-04 | 安徽中铁工程材料科技有限公司 | Method for preparing composite curing agent modified bisphenol F thermosetting adhesive repairing agent special for ballastless track gap and crack damage |
| CN105566183A (en) * | 2016-03-21 | 2016-05-11 | 太原理工大学 | Preparation method of 4,4'-dimercaptodiphenylsulfide |
| CN109721474A (en) * | 2017-10-30 | 2019-05-07 | 中国石油天然气股份有限公司 | A kind of synthetic method of dichloroether and 2- chloroethoxyethanol |
| CN110938401A (en) * | 2019-12-13 | 2020-03-31 | 山东益丰生化环保股份有限公司 | Special adhesive for bulletproof material |
| CN111018756A (en) * | 2019-12-13 | 2020-04-17 | 山东益丰生化环保股份有限公司 | Preparation method of 2-2-dimercaptomethyl-1-3-propanedithiol |
| CN116194540A (en) * | 2020-09-22 | 2023-05-30 | Cht德国有限公司 | Formaldehyde-free printing ink for printing on fabrics |
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Application publication date: 20110608 |