CN104592487B - A kind of be Material synthesis bio-rubber with soybean oil and epoxy soybean oil method - Google Patents
A kind of be Material synthesis bio-rubber with soybean oil and epoxy soybean oil method Download PDFInfo
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Abstract
The invention discloses a kind of method being Material synthesis bio-rubber with soybean oil and epoxy soybean oil.The method, with soybean oil or epoxy soybean oil as raw material, prepares reproducible bio-rubber under the effect of the cross-linking agent containing many sulfydryls.Preparation process of the present invention is simple and safe controlled, and time consumption and energy consumption is few.The most important thing is, the technique raw material sources of this production bio-rubber is extensive, simple and easy to get, and production process, without sulfuration, substantially reduces the production time, saved production cost.
Description
Technical field
The present invention relates to bio-based materials field, a kind of be Material synthesis bio-rubber with soybean oil and epoxy soybean oil method.
Background technology
Rubber is a kind of resilient macromolecular material, due to the performance of its excellence, is widely used in daily life, such as erasing rubber, tire, water wing etc..Rubber is divided into natural rubber and synthetic rubber two kinds, and natural rubber comes from the para ruber of Brazil, and main component is polyisoprene, and synthetic rubber is with coal, oil, the rubber that natural gas etc. is raw material synthetic.According to the prediction of international rubber research group, the whole world to natural rubber and and elastomeric demand will rise to 35,900,000 tons of the year two thousand twenty from 27,600,000 tons of 2013, the demand of the two is roughly equal.
Owing to raw material supply is nervous, make increasingly to come into one's own with biomaterial for the method for Material synthesis rubber, some big companies have attempted to this technology industrialization in the world, the such as Lanxess Corporation of Germany extracts ethanol with reproducible Caulis Sacchari sinensis as raw material, bio-based ethylene is obtained again with ethanol dehydration, and then production ethylene propylene diene rubber, this bio-based ethylene propylene diene rubber can be applicable to automobile industry, building trade and petroleum additive industry.The oil that the Ford Motor Company of the U.S. uses reproducible soybean oil to substitute 25% improves automobile rubber parts, and practice finds that this Semen sojae atricolor filler is expected to replace white carbon black and becomes cheap and eco-friendly rubber reinforcing filler.
But, although the exploitation of bio-rubber achieves some achievements at present, the industrialization cost of bio-rubber is the highest, it is high that one of reason is exactly the prices of raw materials used, and utilization rate is the highest, and production technology is complex, this all will limit large-scale production and the application of bio-rubber.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, it is provided that a kind of be Material synthesis bio-rubber with soybean oil and epoxy soybean oil method.
It is an object of the invention to be achieved through the following technical solutions: a kind of be Material synthesis bio-rubber with soybean oil and epoxy soybean oil method, its step is as follows:
(1) polyepoxy compound of 1 molar part, the triethylamine ring opening catalyst of 0.1-20 molar part, 1-2 molar part list thiocarboxylic acid being dissolved in solvent, the molar concentration of polyepoxy compound is 1 ~ 20mol/L；Reacting under agitation, reaction temperature is 30-80 DEG C, and the response time is 1-24h, removes single thiocarboxylic acid of triethylamine ring opening catalyst, solvent and excess after completion of the reaction, obtains the cross-linking agent containing many sulfydryls；
(2) 1 molar part is contained the cross-linking agent of many sulfydryls, 0.01-20 molar part triethylamine, 0.1-10 molar part epoxy soybean oil, after mix homogeneously, at 30-100 DEG C of cross-linking reaction 1-24 h, put into baking oven inside holding dehydrate after curing molding, obtain bio-rubber；Or after 1 molar part is contained the cross-linking agent of many sulfydryls, 0.01-20 molar part initiator, 0.1-10 molar part soybean oil mix homogeneously, 30-100 DEG C of cross-linking reaction 1-24
H, puts into baking oven inside holding dehydrate, obtains bio-rubber after curing molding.
Further, described polyepoxy compound is by 1,2,7,8-diepoxyoctane, 1, one or more in 2-Ethylene glycol diglycidyl ether, BDDE, triglycidyl isocyanurate, o-phthalic acid diglycidyl ester, glyceryl three-glycidyl ester or four (+)-2,3-Epoxy-1-propanol MDAs, bisphenol A type epoxy resin, bisphenol-s epoxy resin, epoxy-capped PDMS, epoxy soybean oil are according to any proportioning mixing composition.
Further, described single thiocarboxylic acid is made up of according to the mixing of any proportioning for one or more in caprylic acid for n-caproic acid, single sulfur for n Propanoic acid, single thio isobutyrate, single sulfur single thiobenzoate, single thiacetic acid., single sulfur.
Further, described initiator by BPO, AIBN, dialkyl, peroxidating two acyl, tertiary amine, naphthenate, mercaptan, organo-metallic compound such as triethyl aluminum, boron triethyl or naphthoic acid in cuprous one or more according to any proportioning mixing form.
In the cross-linking agent containing many sulfydryls prepared by the present invention, polar functional group is contained on sulfydryl side so that the polarity of sulfydryl is greatly increased so that it is can carry out cross-linking reaction with the soybean oil of relative inertness or epoxy soybean oil.Solve soybean oil or epoxy soybean oil in prior art and be not easy to carry out the technical barrier of cross moulding, be used for preparing bio-rubber relatively costly in traditional handicraft by cheap soybean oil or epoxy soybean oil.Meanwhile, the cross-linking agent containing many sulfydryls of multiple types makes soybean oil or epoxy soybean oil in cross-linking process, and chain length and the degree of cross linking between crosslinking points are controlled, in order to the glass transition temperature of the bio-rubber prepared by regulation and control.
In addition, the preparation method of the present invention is relative to the preparation technology of traditional rubber, with reproducible soybean oil or epoxy soybean oil as raw material, compared to traditional preparation method (the mineral molecule based on non-renewable), there is production process green non-pollution, and without sulfuration, this not only reduces production procedure, and save ordinary rubber and produce required vulcanizing agent, it is a kind of environmental protection rubber production technology easily, and the rubber quality of synthesis is uniform, impurity is few, have good breaking strength.This be raw material production bio-rubber with soybean oil and epoxy soybean oil new technique can carry out large-scale application, the frontier that developing bio-rubber produces.
Accompanying drawing explanation
Fig. 1 is the nuclear-magnetism figure of the thiol crosslinkers prepared by epoxy-capped PDMS；
Fig. 2 is the nuclear-magnetism figure of the thiol crosslinkers prepared by triglycidyl isocyanurate；
Fig. 3 is the nuclear-magnetism figure of the thiol crosslinkers prepared by epoxy resin.
Detailed description of the invention
Tradition rubber typically use synthetic, from oil refine, non-renewable little molecule be prepared, the present invention uses reproducible soybean oil/epoxy soybean oil to prepare bio-rubber, and step is as follows:
(1) polyepoxy compound of 1 molar part, the triethylamine ring opening catalyst of 0.1-20 molar part, 1-2 molar part list thiocarboxylic acid being dissolved in solvent, the molar concentration of polyepoxy compound is 1 ~ 20mol/L；Reacting under agitation, reaction temperature is 30-80 DEG C, and the response time is 1-24h, removes single thiocarboxylic acid of triethylamine ring opening catalyst, solvent and excess after completion of the reaction, obtains the cross-linking agent containing many sulfydryls；The described single thiocarboxylic acid removing triethylamine ring opening catalyst, solvent and excess is prior art, specifically refers to (a kind of sulfhydryl compound containing β-ester base and acetyl grouptransfer synthetic method-201210232801.1 thereof).By in the cross-linking agent containing many sulfydryls that the method obtains, polar functional group is contained on sulfydryl side so that the polarity of sulfydryl is greatly increased so that it is can carry out cross-linking reaction with the soybean oil of relative inertness or epoxy soybean oil.
(2) 1 molar part is contained the cross-linking agent of many sulfydryls, 0.01-20 molar part triethylamine, 0.1-10 molar part epoxy soybean oil, after mix homogeneously, at 30-100 DEG C of cross-linking reaction 1-24 h, put into baking oven inside holding dehydrate after curing molding, obtain bio-rubber；Or after 1 molar part is contained the cross-linking agent of many sulfydryls, 0.01-20 molar part initiator, 0.1-10 molar part soybean oil mix homogeneously, 30-100 DEG C of cross-linking reaction 1-24
H, puts into baking oven inside holding dehydrate, obtains bio-rubber after curing molding.
Described polyepoxy compound is by 1,2,7,8-diepoxyoctane, 1, one or more in 2-Ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, triglycidyl isocyanurate, o-phthalic acid diglycidyl ester, glyceryl three-glycidyl ester or four (+)-2,3-Epoxy-1-propanol MDAs, bisphenol A type epoxy resin, bisphenol-s epoxy resin, epoxy-capped PDMS, epoxy soybean oil are according to any proportioning mixing composition.
Described single thiocarboxylic acid is made up of according to the mixing of any proportioning for one or more in caprylic acid for n-caproic acid, single sulfur for n Propanoic acid, single thio isobutyrate, single sulfur single thiobenzoate, single thiacetic acid., single sulfur.
Described initiator by BPO, AIBN, dialkyl, peroxidating two acyl, tertiary amine, naphthenate, mercaptan, organo-metallic compound such as triethyl aluminum, boron triethyl or naphthoic acid in cuprous one or more according to any proportioning mixing form.
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
1) polyepoxy compound of 1 mole, the triethylamine ring opening catalyst of 0.1 mole, 1 mole of single thiocarboxylic acid being dissolved in the methanol of 1L, react 1 h under agitation, reaction temperature is 30 DEG C；Solvent is evaporated off with rotation after completion of the reaction, is then extracted with ethyl acetate, the NaHCO of 1mol/L3Solution cleans the single thiocarboxylic acid removing excess, and the dilute hydrochloric acid of 1mol/L cleans removes triethylamine, and washing, anhydrous magnesium sulfate revolves after drying and boils off except solvent, obtains the cross-linking agent containing many sulfydryls；The nuclear-magnetism figure of this cross-linking agent is as it is shown in figure 1, it can be seen that on sulfydryl side with the presence of highly polar oxygen ester so that sulfydryl polarity becomes big, and activity increases, it is ensured that the follow-up reaction with inert epoxy soybean oil, to synthesize reproducible bio-rubber.
2) cross-linking agent and 0.01 mole of triethylamine, 0.1 mole of epoxy soybean oil mixing of sulfydryl more than 1 mole are carried out heat cross-linking and react 1 h, baking oven inside holding dehydrate is put into after curing molding, obtain bio-rubber, reaction temperature is 30 DEG C, put into baking oven inside holding dehydrate after curing molding, obtain bio-rubber.
Described multi-epoxy epoxide is epoxy-capped PDMS.Described single thiocarboxylic acid is single thiobenzoate.Described initiator is BPO.
Embodiment 2
1) polyepoxy compound of 1 molar part, the triethylamine ring opening catalyst of 20 moles, 2 moles of single thiocarboxylic acids are dissolved in the ethanol of 20L, at 80 DEG C, stir response time 24 h, carry out post processing according to embodiment 1 after completion of the reaction and obtain the cross-linking agent containing many sulfydryls；
2) 1 mole of sulfhydryl modified epoxide and 20 mole of triethylamine, 10 moles of epoxy soybean oil mixing being carried out heat cross-linking and react 24 h, reaction temperature is 100 DEG C, puts into baking oven inside holding dehydrate, obtain bio-rubber after curing molding.
Described multi-epoxy epoxide is 1,2-Ethylene glycol diglycidyl ether.Described single thiocarboxylic acid is selected from single thiacetic acid..Described initiator is AIBN.
Embodiment 3
1) polyepoxy compound of 1 mole, the triethylamine ring opening catalyst of 10 molar part, 1.5 molar part list thiocarboxylic acids are dissolved in the dichloromethane of 5L, at 60 DEG C, stirring reaction 12 h, carry out post processing according to embodiment 1 after completion of the reaction and obtain the cross-linking agent containing many sulfydryls；
2) 1 mole of sulfhydryl modified epoxide and 10 mole of triethylamine, 5 moles of epoxy soybean oil mixing being carried out heat cross-linking, reaction temperature is 60 DEG C, and the response time is 12 h, puts into baking oven inside holding dehydrate, obtain bio-rubber after curing molding.
Described multi-epoxy epoxide is 1,4-butanediol diglycidyl ether.Described single thiocarboxylic acid is that single sulfur is for n Propanoic acid.Described initiator is dialkyl.
Embodiment 4
1) polyepoxy compound of 1 mole, the triethylamine ring opening catalyst of 2 moles, 1 mole of single thiocarboxylic acid are dissolved in the ether of 1L, at 34 DEG C, stir response time 2 h, carry out post processing according to embodiment 1 after completion of the reaction and obtain the cross-linking agent containing many sulfydryls；
2) 1 mole of sulfhydryl modified epoxide and 6 mole of triethylamine, 0.6 mole of epoxy soybean oil mixing are carried out heat cross-linking reaction, reaction temperature is 67 DEG C, response time is 2 h, puts into baking oven inside holding dehydrate, obtain bio-rubber after curing molding.
Described multi-epoxy epoxide includes triglycidyl isocyanurate.Described single thiocarboxylic acid is single thio isobutyrate.Described initiator is peroxidating two acyl.
As shown in Figure 2, on sulfydryl side with the presence of highly polar oxygen ester so that sulfydryl polarity becomes big, and activity increases, it is ensured that the preparation of subsequent bio base rubber.
Embodiment 5
1) polyepoxy compound of 1 mole, the triethylamine ring opening catalyst of 6 moles, 1.2 moles of single thiocarboxylic acids are dissolved in the ethyl acetate of 15L, at 42 DEG C, stirring reaction 4 h, carry out post processing according to embodiment 1 after completion of the reaction and obtain the cross-linking agent containing many sulfydryls；
2) 1 mole of sulfhydryl modified epoxide and 8 mole of triethylamine, 1.3 moles of epoxy soybean oil mixing being carried out heat cross-linking reaction, react 4h, reaction temperature is 72 DEG C, puts into baking oven inside holding dehydrate, obtain bio-rubber after curing molding.
Described multi-epoxy epoxide is o-phthalic acid diglycidyl ester.Described single thiocarboxylic acid is single thiobenzoate.Described initiator is tertiary amine.
Embodiment 6
1) polyepoxy compound of 1 mole, the triethylamine ring opening catalyst of 13 moles, 1.5 moles of single thiocarboxylic acids are dissolved in the N-Methyl pyrrolidone of 10L, at 60 DEG C, react 14 h, carry out post processing according to embodiment 1 after completion of the reaction and obtain the cross-linking agent containing many sulfydryls；
2) 1 mole of sulfhydryl modified epoxide and 13 mole of triethylamine, 7 moles of epoxy soybean oil mixing being carried out heat cross-linking and react 14 h, reaction temperature is 80 DEG C, puts into baking oven inside holding dehydrate, obtain bio-rubber after curing molding.
Described multi-epoxy epoxide is glyceryl three-glycidyl ester.Described single thiocarboxylic acid is selected from single sulfur for n-caproic acid.Described initiator is selected from naphthenate.
Embodiment 7
1) polyepoxy compound of 1 mole, the triethylamine ring opening catalyst of 16 moles, 1.8 moles of single thiocarboxylic acids are dissolved in 10L by N, in the mixed solution that dinethylformamide and dimethyl sulfoxide form according to volume ratio 1:1, response time 18 h at 70 DEG C, carries out post processing according to embodiment 1 after completion of the reaction and obtains the cross-linking agent containing many sulfydryls；
2) 1 mole of sulfhydryl modified epoxide and 17 mole of triethylamine, 8 moles of epoxy soybean oil mixing being carried out heat cross-linking and react 17 h, reaction temperature is 87 DEG C, puts into baking oven inside holding dehydrate, obtain bio-rubber after curing molding.
Described multi-epoxy epoxide includes four (+)-2,3-Epoxy-1-propanol MDAs.Described single thiocarboxylic acid is that single sulfur is for caprylic acid.Described initiator is triethyl aluminum.
Embodiment 8
1) polyepoxy compound of 1 mole, the triethylamine ring opening catalyst of 19 moles, 1.2 moles of single thiocarboxylic acids are dissolved in the toluene of 2L, at 50 DEG C, stirring reaction 21 h, carry out post processing according to embodiment 1 after completion of the reaction and obtain the cross-linking agent containing many sulfydryls；
2) 1 mole of sulfhydryl modified epoxide and 7 mole of triethylamine, 4 moles of epoxy soybean oil mixing being carried out heat cross-linking and react 6 h, reaction temperature is 100 DEG C, puts into baking oven inside holding dehydrate, obtain bio-rubber after curing molding.
Described multi-epoxy epoxide includes bisphenol A type epoxy resin.Described single thiocarboxylic acid is that single sulfur is for n-caproic acid.Described initiator is boron triethyl.
From the figure 3, it may be seen that on sulfydryl side with the presence of highly polar oxygen ester so that sulfydryl polarity becomes big, and activity increases, it is ensured that the preparation of subsequent bio base rubber.
Embodiment 9
1) polyepoxy compound of 1 mole, the triethylamine ring opening catalyst of 11 moles, 1.5 moles of single thiocarboxylic acids are dissolved in the oxolane of 6L, at 39 DEG C, stirring reaction 14 h, carry out post processing according to embodiment 1 after completion of the reaction and obtain the cross-linking agent containing many sulfydryls；
2) 1 mole of sulfhydryl modified epoxide and 15 mole of triethylamine, 7 moles of epoxy soybean oil mixing being carried out heat cross-linking and react 13 h, reaction temperature is 60 DEG C, puts into baking oven inside holding dehydrate, obtain bio-rubber after curing molding.
Described multi-epoxy epoxide includes bisphenol-s epoxy resin.Described single thiocarboxylic acid is single thiacetic acid..Described initiator is that naphthoic acid is cuprous.
Embodiment 10
1) by the polyepoxy compound of 1 mole, the triethylamine ring opening catalyst of 17 moles, 1.9 moles of single thiocarboxylic acid solvents in the hexane of 12L, at 70 DEG C, react 14 h, carry out post processing according to embodiment 1 after completion of the reaction and obtain the cross-linking agent containing many sulfydryls；
2) 1 mole of sulfhydryl modified epoxide and 12 mole of triethylamine, 7 moles of epoxy soybean oil mixing being carried out heat cross-linking and react 23 h, reaction temperature is 50 DEG C, puts into baking oven inside holding dehydrate, obtain bio-rubber after curing molding.
Described multi-epoxy epoxide is epoxy soybean oil.Described single thiocarboxylic acid is that single sulfur is for caprylic acid.Described initiator is BPO.
Embodiment 11
1) polyepoxy compound of 1 mole, the triethylamine ring opening catalyst of 0.1 mole, 1 mole of single thiocarboxylic acid are dissolved in the N of 15L, in N-dimethyl acetylamide, at 30 DEG C, react 1 h, carry out post processing according to embodiment 1 after completion of the reaction and obtain the cross-linking agent containing many sulfydryls；
2) 1 mole of sulfhydryl modified epoxide and 0.01 molar part initiator, 0.1 mole of epoxy soybean oil mixing are carried out heat cross-linking reaction, baking oven inside holding dehydrate is put into after curing molding, obtain bio-rubber 1 h, reaction temperature is 30 DEG C, put into baking oven inside holding dehydrate after curing molding, obtain bio-rubber.
Described multi-epoxy epoxide is 1,2,7,8-diepoxyoctane.Described single thiocarboxylic acid is selected from single thiobenzoate.Described initiator is BPO.
Embodiment 12
1) polyepoxy compound of 1 mole, the triethylamine ring opening catalyst of 20 moles, 2 moles of single thiocarboxylic acids are dissolved in the mixed solution that 15L is made up of according to volume ratio 2:1 chloroform and dichloromethane, at 80 DEG C, react 24 h, carry out post processing according to embodiment 1 after completion of the reaction and obtain the cross-linking agent containing many sulfydryls；
2) 1 mole of sulfhydryl modified epoxide and 20 mole initiator, 10 moles of epoxy soybean oil mixing being carried out heat cross-linking and react 24 h, reaction temperature is 100 DEG C, puts into baking oven inside holding dehydrate, obtain bio-rubber after curing molding.
Described multi-epoxy epoxide is 1,2-Ethylene glycol diglycidyl ether.Described single thiocarboxylic acid is selected from single thiacetic acid..Described initiator is AIBN.
Embodiment 13
1) polyepoxy compound of 1 mole, the triethylamine ring opening catalyst of 10 moles, 1.5 moles of single thiocarboxylic acids are dissolved in the oxolane of 6L, at 60 DEG C, react 12 h, carry out post processing according to embodiment 1 after completion of the reaction and obtain the cross-linking agent containing many sulfydryls；
2) 1 mole of sulfhydryl modified epoxide and 10 mole initiator, 5 moles of epoxy soybean oil mixing being carried out heat cross-linking, reaction temperature is 60 DEG C, and the response time is 12 h, puts into baking oven inside holding dehydrate, obtain bio-rubber after curing molding.
Described multi-epoxy epoxide is 1,4-butanediol diglycidyl ether.Described single thiocarboxylic acid is that single sulfur is for n Propanoic acid.Described initiator is dialkyl.
Embodiment 14
1) polyepoxy compound of 1 mole, the triethylamine ring opening catalyst of 2 moles, 1 mole of single thiocarboxylic acid are dissolved in the oxolane of 10L, at 34 DEG C, react 2 h, carry out post processing according to embodiment 1 after completion of the reaction and obtain the cross-linking agent containing many sulfydryls；
2) 1 mole of sulfhydryl modified epoxide and 6 mole initiator, 0.6 mole of epoxy soybean oil mixing are carried out heat cross-linking reaction, reaction temperature is 67 DEG C, response time is 2 h, puts into baking oven inside holding dehydrate, obtain bio-rubber after curing molding.
Described multi-epoxy epoxide includes triglycidyl isocyanurate.Described single thiocarboxylic acid is single thio isobutyrate.Described initiator is peroxidating two acyl.
Embodiment 15
1) polyepoxy compound of 1 mole, the triethylamine ring opening catalyst of 6 moles, 1.2 moles of single thiocarboxylic acids are dissolved in the ethyl acetate of 1L, at 42 DEG C, stirring reaction 4 h, carry out post processing according to embodiment 1 after completion of the reaction and obtain the cross-linking agent containing many sulfydryls；
2) 1 mole of sulfhydryl modified epoxide and 8 mole initiator, 1.3 moles of epoxy soybean oil mixing being carried out heat cross-linking reaction, react 4h, reaction temperature is 72 DEG C, puts into baking oven inside holding dehydrate, obtain bio-rubber after curing molding.
Described multi-epoxy epoxide is o-phthalic acid diglycidyl ester.Described single thiocarboxylic acid is single thiobenzoate.Described initiator is tertiary amine.
Embodiment 16
1) polyepoxy compound of 1 mole, the triethylamine ring opening catalyst of 13 moles, 1.5 moles of single thiocarboxylic acids are dissolved in the ethyl acetate of 1L, at 60 DEG C, stirring reaction 14 h, carry out post processing according to embodiment 1 after completion of the reaction and obtain the cross-linking agent containing many sulfydryls；
2) 1 mole of sulfhydryl modified epoxide and 13 mole initiator, 7 moles of epoxy soybean oil mixing being carried out heat cross-linking and react 14 h, reaction temperature is 80 DEG C, puts into baking oven inside holding dehydrate, obtain bio-rubber after curing molding.
Described multi-epoxy epoxide is glyceryl three-glycidyl ester.Described single thiocarboxylic acid is selected from single sulfur for n-caproic acid.Described initiator is selected from naphthenate.
Embodiment 17
1) polyepoxy compound of 1 mole, the triethylamine ring opening catalyst of 16 moles, 1.8 moles of single thiocarboxylic acids are dissolved in the toluene of 3L, at 70 DEG C, stirring reaction 18 h, carry out post processing according to embodiment 1 the most after completion of the reaction and obtain the cross-linking agent containing many sulfydryls；
2) 1 mole of sulfhydryl modified epoxide and 17 mole initiator, 8 moles of epoxy soybean oil mixing being carried out heat cross-linking and react 17 h, reaction temperature is 87 DEG C, puts into baking oven inside holding dehydrate, obtain bio-rubber after curing molding.
Described multi-epoxy epoxide includes four (+)-2,3-Epoxy-1-propanol MDAs.Described single thiocarboxylic acid is that single sulfur is for caprylic acid.Described initiator is triethyl aluminum.
Embodiment 18
1) polyepoxy compound of 1 mole, the triethylamine ring opening catalyst of 19 moles, 1.2 moles of single thiocarboxylic acids are dissolved in the toluene of 3L, at 50 DEG C, stirring reaction 21 h, carry out post processing according to embodiment 1 after completion of the reaction and obtain the cross-linking agent containing many sulfydryls；
2) 1 mole of sulfhydryl modified epoxide and 7 mole initiator, 4 moles of epoxy soybean oil mixing being carried out heat cross-linking and react 6 h, reaction temperature is 100 DEG C, puts into baking oven inside holding dehydrate, obtain bio-rubber after curing molding.
Described multi-epoxy epoxide includes bisphenol A type epoxy resin.Described single thiocarboxylic acid is that single sulfur is for n-caproic acid.Described initiator is boron triethyl.
Embodiment 19
1) polyepoxy compound of 1 mole, the triethylamine ring opening catalyst of 11 moles, 1.5 moles of single thiocarboxylic acids are dissolved in the toluene of 3L, at 39 DEG C, stirring reaction 14 h, carry out post processing according to embodiment 1 after completion of the reaction and obtain the cross-linking agent containing many sulfydryls；
2) 1 mole of sulfhydryl modified epoxide and 15 mole initiator, 7 moles of epoxy soybean oil mixing being carried out heat cross-linking and react 13 h, reaction temperature is 60 DEG C, puts into baking oven inside holding dehydrate, obtain bio-rubber after curing molding.
Described multi-epoxy epoxide includes bisphenol-s epoxy resin.Described single thiocarboxylic acid is single thiacetic acid..Described initiator is that naphthoic acid is cuprous.
Embodiment 20
1) polyepoxy compound of 1 mole, the triethylamine ring opening catalyst of 17 moles, 1.9 moles of single thiocarboxylic acids are dissolved in the toluene of 3L, at 70 DEG C, react 14 h, carry out post processing according to embodiment 1 after completion of the reaction and obtain the cross-linking agent containing many sulfydryls；
2) 1 mole of sulfhydryl modified epoxide and 12 mole initiator, 7 moles of epoxy soybean oil mixing being carried out heat cross-linking and react 23 h, reaction temperature is 50 DEG C, puts into baking oven inside holding dehydrate, obtain bio-rubber after curing molding.
Described multi-epoxy epoxide is epoxy soybean oil.Described single thiocarboxylic acid is that single sulfur is for caprylic acid.Described initiator is BPO.
Embodiment 21
1) polyepoxy compound of 1 mole, the triethylamine ring opening catalyst of 0.1 molar part, 1 molar part list thiocarboxylic acid are dissolved in the toluene of 3L；At 30 DEG C, stirring reaction 14h, carries out post processing according to embodiment 1 after completion of the reaction and obtains the cross-linking agent containing many sulfydryls.
(2) 1 molar part is contained the cross-linking agent of many sulfydryls, 0.20 molar part triethylamine, 10 molar part epoxy soybean oils, after mix homogeneously, at 100 DEG C of cross-linking reaction 14 h, put into baking oven inside holding dehydrate after curing molding, obtain bio-rubber.
Described polyepoxy compound is 1,2,7,8-diepoxyoctane, 1,2-Ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, triglycidyl isocyanurate.Its molar ratio is: 1:6:3:5.
Described single thiocarboxylic acid by single thiobenzoate, single thiacetic acid., single sulfur for n Propanoic acid.Its molar ratio is: 1:3:
4。
Described initiator is by BPO, AIBN, dialkyl, peroxidating two acyl.Its molar ratio is: 1:1:3:2.
Embodiment 22
1) polyepoxy compound of 1 mole, the triethylamine ring opening catalyst of 0.1 molar part, 1 molar part list thiocarboxylic acid are dissolved in the oxolane of 1L；At 30 DEG C, stirring reaction 1h, carries out post processing according to embodiment 1 after completion of the reaction and obtains the cross-linking agent containing many sulfydryls.
(2) 1 molar part is contained the cross-linking agent of many sulfydryls, 20 molar part triethylamines, 10 molar part epoxy soybean oils, after mix homogeneously, at 30 DEG C of cross-linking reaction 4 h, put into baking oven inside holding dehydrate after curing molding, obtain bio-rubber.
Described polyepoxy compound is glyceryl three-glycidyl ester, bisphenol A type epoxy resin, bisphenol-s epoxy resin, epoxy-capped PDMS, epoxy soybean oil.Its molar ratio is: 1:2:3:5:2.
Described single thiocarboxylic acid by single sulfur for n-caproic acid, single sulfur for caprylic acid.Its molar ratio is: 1:2.
Described initiator is by tertiary amine, naphthenate, mercaptan, triethyl aluminum.Its molar ratio is: 1:5:3:1.
Embodiment 23
1) polyepoxy compound of 1 mole, the triethylamine ring opening catalyst of 0.3 molar part, 5 molar part list thiocarboxylic acids are dissolved in the oxolane of 1L；Reacting under agitation, reaction temperature is 80 DEG C, and the response time is 4h, carries out post processing according to embodiment 1 after completion of the reaction and obtains the cross-linking agent containing many sulfydryls.
(2) 1 molar part is contained the cross-linking agent of many sulfydryls, 3 molar part triethylamines, 2 molar part epoxy soybean oils, after mix homogeneously, at 60 DEG C of cross-linking reaction 6 h, put into baking oven inside holding dehydrate after curing molding, obtain bio-rubber.
Described polyepoxy compound is glycidyl chlorinated isocyanurates, o-phthalic acid diglycidyl ester.Its molar ratio is: 1:5.
Described single thiocarboxylic acid is that single thiacetic acid., single sulfur are for n Propanoic acid.Its molar ratio is 1:2.
Described initiator is by BPO, peroxidating two acyl.Its molar ratio is: 1:7.
Embodiment 24
1) polyepoxy compound of 1 mole, the triethylamine ring opening catalyst of 3 molar part, 7 molar part list thiocarboxylic acids are dissolved in the oxolane of 1L；Reacting under agitation, reaction temperature is 70 DEG C, and the response time is 13h, carries out post processing according to embodiment 1 after completion of the reaction and obtains the cross-linking agent containing many sulfydryls.
(2) 1 molar part is contained the cross-linking agent of many sulfydryls, 10 molar part triethylamines, 7 molar part epoxy soybean oils, after mix homogeneously, at 80 DEG C of cross-linking reaction 9 h, put into baking oven inside holding dehydrate after curing molding, obtain bio-rubber.
Described polyepoxy compound is 1,2,7,8-diepoxyoctane, 1,4-butanediol diglycidyl ether.Its molar ratio is: 1:3.
Described single thiocarboxylic acid by single thiacetic acid., single sulfur for n Propanoic acid.Its molar ratio is: 1:9.
Described initiator is by AIBN.Its molar ratio is: 1:3.
Above-described embodiment is used for illustrating the present invention rather than limiting the invention, in the protection domain of spirit and claims of the present invention, and any modifications and changes that the present invention is made, both fall within protection scope of the present invention.
Claims (4)
1. the method that a kind is Material synthesis bio-rubber with soybean oil and epoxy soybean oil, it is characterised in that
Its step is as follows:
(1) by the polyepoxy compound of 1 molar part, the triethylamine ring opening catalyst of 0.1-20 molar part, 1-2
Molar part list thiocarboxylic acid is dissolved in solvent, and the molar concentration of polyepoxy compound is 1～20mol/L；Stirring
Reacting under the conditions of mixing, reaction temperature is 30-80 DEG C, and the response time is 1-24h, removes three second after completion of the reaction
Single thiocarboxylic acid of amine ring opening catalyst, solvent and excess, obtains the cross-linking agent containing many sulfydryls；Described molten
Agent by methanol, ethanol, isopropanol, toluene, benzene, chloroform, dichloromethane, oxolane, dioxane,
Hexane, ether, ethyl acetate, N-Methyl pyrrolidone, DMF, N, N-dimethyl
One or more in acetamide, dimethyl sulfoxide are according to any proportioning mixing composition；
(2) 1 molar part is contained the cross-linking agent of many sulfydryls, 0.01-20 molar part triethylamine, 0.1-10 mole
Part epoxy soybean oil, after mix homogeneously, 30-100 DEG C of cross-linking reaction 1-24h, puts into baking oven after curing molding
Inside holding dehydrate, obtains bio-rubber；Or 1 molar part is contained the cross-linking agent of many sulfydryls, 0.01-20
After molar part initiator, 0.1-10 molar part soybean oil mix homogeneously, 30-100 DEG C of cross-linking reaction 1-24h,
Put into baking oven inside holding dehydrate after curing molding, obtain bio-rubber.
One the most according to claim 1 is with soybean oil and epoxy soybean oil for Material synthesis bio-based rubber
The method of glue, it is characterised in that described polyepoxy compound by 1,2,7,8-diepoxyoctane, 1，2-ethandiol
Diglycidyl ether, 1,4-butanediol diglycidyl ether, tri epoxy propyl isocyanurate, phthalic acid
2-glycidyl ester, glyceryl three-glycidyl ester or four (+)-2,3-Epoxy-1-propanol MDAs, bisphenol A-type
One or many in epoxy resin, bisphenol-s epoxy resin, epoxy-capped PDMS, epoxy soybean oil
Plant according to any proportioning mixing composition.
One the most according to claim 1 is with soybean oil and epoxy soybean oil for Material synthesis bio-based rubber
The method of glue, it is characterised in that described single thiocarboxylic acid is by single thiobenzoate, single thiacetic acid., single sulfur
For n Propanoic acid, single thio isobutyrate, single sulfur for n-caproic acid, single sulfur for one or more in caprylic acid according to
Arbitrarily proportioning mixing composition.
The most according to claim 1 a kind of be Material synthesis bio-rubber with soybean oil method, its
Be characterised by, described initiator by BPO, AIBN, dialkyl, peroxidating two acyl, tertiary amine,
One or more in naphthenate, mercaptan, organo-metallic compound are according to any proportioning mixing composition.
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