CN104592487A - Method for synthesizing biological base rubber by using soybean oil and epoxidized soybean oil as raw materials - Google Patents
Method for synthesizing biological base rubber by using soybean oil and epoxidized soybean oil as raw materials Download PDFInfo
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Abstract
The invention discloses a method for synthesizing biological base rubber by using soybean oil and epoxidized soybean oil as raw materials. According to the method, the soybean oil or the epoxidized soybean oil is used as raw materials, and renewable biological base rubber can be prepared under the action of a crosslinking agent containing multiple sulfhydryl groups. The method disclosed by the invention is simple, safe and controllable in preparation process and low in time and energy consumption. Most importantly, the process for producing the biological base rubber is wide, simple and easily available in raw material source, the production process does not need vulcanization, the production time is greatly shortened, and the production cost is saved.
Description
Technical field
The present invention relates to bio-based materials field, particularly a kind of method that is Material synthesis bio-rubber with soybean oil and epoxy soybean oil.
Background technology
Rubber is a kind of resilient macromolecular material, due to the performance of its excellence, is widely used in daily life, as eraser, and 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, and Sweet natural gas etc. are the rubber of 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 3,590 ten thousand tons of the year two thousand twenty from 2013 2,760 ten thousand tons, the demand of the two is roughly equal.
Because raw material supply is nervous, make to be that the method for Material synthesis rubber more and more comes into one's own with biomaterial, some big companies have attempted this technology industrialization in the world, such as the Lanxess Corporation of Germany extracts ethanol with reproducible sugarcane as starting material, bio-based ethene is obtained again with ethanol dehydration, and then production terpolymer EP rubber, this bio-based terpolymer EP rubber can be applicable to automobile industry, building trade and petroleum additive industry.The Ford Motor Company of the U.S. uses reproducible soybean oil to substitute the oil of 25% to improve automobile rubber component, and practice finds that this soybean weighting agent is expected to replace 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 still very high, it is high that one of reason is exactly the prices of raw and semifnished materials used, and utilization ratio is not high, and production technique is comparatively complicated, this is all by the scale operation of restriction bio-rubber and application.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of method being Material synthesis bio-rubber with soybean oil and epoxy soybean oil is provided.
The object of the invention is to be achieved through the following technical solutions: a kind of method that is Material synthesis bio-rubber with soybean oil and epoxy soybean oil, its step is as follows:
(1) be dissolved in solvent by the triethylamine ring opening catalyst of the polyepoxy compound of 1 molar part, 0.1-20 molar part, 1-2 molar part list thiocarboxylic acid, the volumetric molar concentration of polyepoxy compound is 1 ~ 20mol/L; React under agitation, temperature of reaction is 30-80 DEG C, and the reaction times is 1-24h, removes triethylamine ring opening catalyst, solvent and excessive single thiocarboxylic acid after completion of the reaction, obtains the linking agent containing many sulfydryls;
(2) 1 molar part is contained the linking agent of many sulfydryls, 0.01-20 molar part triethylamine, 0.1-10 molar part epoxy soybean oil, after mixing, at 30-100 DEG C of crosslinking reaction 1-24 h, put into baking oven inside holding after curing molding and dehydrate, obtain bio-rubber; Or 1 molar part contained the linking agent of many sulfydryls, after 0.01-20 molar part initiator, 0.1-10 molar part soybean oil mix, at 30-100 DEG C of crosslinking reaction 1-24 h, put into baking oven inside holding after curing molding and dehydrate, obtain bio-rubber.
Further, described polyepoxy compound is by 1,2,7,8-diepoxyoctane, 1, one or more in 2-ethylene glycol diglycidylether, BDDE, triglycidyl isocyanurate, o-phthalic acid diglycidyl ester, glyceryl three-glycidyl ester or four Racemic glycidol diaminodiphenylmethane, 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 any proportioning mixing one or more in single thiobenzoic acid, single thioacetic acid, single sulfo-n Propanoic acid, single thio isobutyrate, single sulfo-n-caproic acid, single sulfo-n-caprylic acid.
Further, one or more during described initiator is as cuprous in triethyl aluminum, triethyl-boron or naphthoic acid by BPO, AIBN, dialkyl, peroxidation two acyl, tertiary amine, naphthenate, mercaptan, organometallic compound mix according to any proportioning and form.
Containing in the linking agent of many sulfydryls prepared by the present invention, polar functional group is contained on sulfydryl side, and the polarity of sulfydryl is increased greatly, can carry out crosslinking reaction with the soybean oil of relative inertness or epoxy soybean oil.Solve the technical barrier that soybean oil or epoxy soybean oil in prior art are not easy to carry out cross moulding, by the soybean oil of cheapness or epoxy soybean oil for the preparation of the higher bio-rubber of cost in traditional technology.Meanwhile, multiple types make soybean oil or epoxy soybean oil in cross-linking process containing the linking agent of many sulfydryls, the chain length between cross-linking set and degree of crosslinking controlled so that the second-order transition temperature of bio-rubber prepared by regulation and control.
In addition, preparation method of the present invention is relative to the preparation technology of traditional rubber, with reproducible soybean oil or epoxy soybean oil for raw material, compared to traditional preparation method's (mineral molecule based on non-renewable), there is production process green non-pollution, and without the need to sulfuration, this not only reduces Production Flow Chart, and save ordinary rubber and produce required vulcanizing agent, be a kind of environmental protection rubber production technology easily, and the rubber quality of synthesis is even, impurity is few, have good tensile strength at yield.This new technology being raw material production bio-rubber with soybean oil and epoxy soybean oil can carry out large-scale application, the frontier that developing bio-rubber is produced.
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.
Embodiment
Conventional rubber generally adopt synthetic, refine from oil, non-renewable small molecules is prepared, the present invention adopts reproducible soybean oil/epoxy soybean oil to prepare bio-rubber, and step is as follows:
(1) be dissolved in solvent by the triethylamine ring opening catalyst of the polyepoxy compound of 1 molar part, 0.1-20 molar part, 1-2 molar part list thiocarboxylic acid, the volumetric molar concentration of polyepoxy compound is 1 ~ 20mol/L; React under agitation, temperature of reaction is 30-80 DEG C, and the reaction times is 1-24h, removes triethylamine ring opening catalyst, solvent and excessive single thiocarboxylic acid after completion of the reaction, obtains the linking agent containing many sulfydryls; Described to remove triethylamine ring opening catalyst, solvent and excessive single thiocarboxylic acid be prior art, specifically can with reference to (a kind of sulfhydryl compound containing β-ester base and acetyl grouptransfer synthetic method-201210232801.1 thereof).What obtained by the method is contained in the linking agent of many sulfydryls, and polar functional group is contained on sulfydryl side, and the polarity of sulfydryl is increased greatly, can carry out crosslinking reaction with the soybean oil of relative inertness or epoxy soybean oil.
(2) 1 molar part is contained the linking agent of many sulfydryls, 0.01-20 molar part triethylamine, 0.1-10 molar part epoxy soybean oil, after mixing, at 30-100 DEG C of crosslinking reaction 1-24 h, put into baking oven inside holding after curing molding and dehydrate, obtain bio-rubber; Or 1 molar part contained the linking agent of many sulfydryls, after 0.01-20 molar part initiator, 0.1-10 molar part soybean oil mix, at 30-100 DEG C of crosslinking reaction 1-24 h, put into baking oven inside holding after curing molding and dehydrate, obtain bio-rubber.
Described polyepoxy compound is by 1,2,7,8-diepoxyoctane, 1, one or more in 2-ethylene glycol diglycidylether, BDDE, triglycidyl isocyanurate, o-phthalic acid diglycidyl ester, glyceryl three-glycidyl ester or four Racemic glycidol diaminodiphenylmethane, 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 any proportioning mixing one or more in single thiobenzoic acid, single thioacetic acid, single sulfo-n Propanoic acid, single thio isobutyrate, single sulfo-n-caproic acid, single sulfo-n-caprylic acid.
One or more during described initiator is as cuprous in triethyl aluminum, triethyl-boron or naphthoic acid by BPO, AIBN, dialkyl, peroxidation two acyl, tertiary amine, naphthenate, mercaptan, organometallic compound mix according to any proportioning and form.
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
1) be dissolved in the methyl alcohol of 1L by the polyepoxy compound of 1 mole, the triethylamine ring opening catalyst of 0.1 mole, 1 mole of single thiocarboxylic acid, react 1 h under agitation, temperature of reaction is 30 DEG C; Steaming except desolventizing with revolving after completion of the reaction, being then extracted with ethyl acetate, the NaHCO of 1mol/L
3excessive single thiocarboxylic acid is removed in solution cleaning, and the dilute hydrochloric acid cleaning of 1mol/L removes triethylamine, washing, revolves to boil off to desolventize after anhydrous magnesium sulfate drying, obtains the linking agent containing many sulfydryls; The nuclear-magnetism figure of this linking agent as shown in Figure 1, as can be seen from the figure, has the oxygen ester of strong polarity to exist on sulfydryl side, make sulfydryl polarity become large, active increase, ensure that reaction that the is follow-up and epoxy soybean oil of inertia, to synthesize reproducible bio-rubber.
2) linking agent of sulfydryl more than 1 mole and 0.01 mole of triethylamine, 0.1 mole of epoxy soybean oil mixing are carried out heat cross-linking and react 1 h, put into baking oven inside holding after curing molding to dehydrate, obtain bio-rubber, temperature of reaction is 30 DEG C, put into baking oven inside holding after curing molding to dehydrate, obtain bio-rubber.
Described multi-epoxy epoxy compounds is epoxy-capped PDMS.Described single thiocarboxylic acid is single thiobenzoic acid.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, stirring reaction time 24 h at 80 DEG C, carries out according to embodiment 1 linking agent that aftertreatment obtains containing many sulfydryls after completion of the reaction;
2) 1 mole of sulfhydryl modified epoxy compounds and 20 mole of triethylamine, 10 moles of epoxy soybean oil mixing are carried out heat cross-linking and react 24 h, temperature of reaction is 100 DEG C, puts into baking oven inside holding and dehydrates, obtain bio-rubber after curing molding.
Described multi-epoxy epoxy compounds is 1，2-ethandiol diglycidylether.Described single thiocarboxylic acid is selected from single thioacetic acid.Described initiator is AIBN.
Embodiment 3
1) the triethylamine ring opening catalyst of the polyepoxy compound of 1 mole, 10 molar part, 1.5 molar part list thiocarboxylic acids are dissolved in the methylene dichloride of 5L, stirring reaction 12 h at 60 DEG C, carries out according to embodiment 1 linking agent that aftertreatment obtains containing many sulfydryls after completion of the reaction;
2) 1 mole of sulfhydryl modified epoxy compounds and 10 mole of triethylamine, 5 moles of epoxy soybean oils mixing are carried out heat cross-linking, temperature of reaction is 60 DEG C, reaction times is 12 h, puts into baking oven inside holding and dehydrates, obtain bio-rubber after curing molding.
Described multi-epoxy epoxy compounds is BDDE.Described single thiocarboxylic acid is single sulfo-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, stirring reaction time 2 h at 34 DEG C, carries out according to embodiment 1 linking agent that aftertreatment obtains containing many sulfydryls after completion of the reaction;
2) 1 mole of sulfhydryl modified epoxy compounds and 6 mole of triethylamine, 0.6 mole of epoxy soybean oil mixing are carried out heat cross-linking reaction, temperature of reaction is 67 DEG C, reaction times is 2 h, puts into baking oven inside holding and dehydrates, obtain bio-rubber after curing molding.
Described multi-epoxy epoxy compounds comprises triglycidyl isocyanurate.Described single thiocarboxylic acid is single thio isobutyrate.Described initiator is peroxidation two acyl.
As shown in Figure 2, have the oxygen ester of strong polarity to exist on sulfydryl side, make sulfydryl polarity become large, active increase, ensure 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, stirring reaction 4 h at 42 DEG C, carries out according to embodiment 1 linking agent that aftertreatment obtains containing many sulfydryls after completion of the reaction;
2) 1 mole of sulfhydryl modified epoxy compounds and 8 mole of triethylamine, 1.3 moles of epoxy soybean oils mixing are carried out heat cross-linking reaction, reaction 4h, temperature of reaction is 72 DEG C, puts into baking oven inside holding and dehydrates, obtain bio-rubber after curing molding.
Described multi-epoxy epoxy compounds is o-phthalic acid diglycidyl ester.Described single thiocarboxylic acid is single thiobenzoic acid.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 according to embodiment 1 linking agent that aftertreatment obtains containing many sulfydryls after completion of the reaction;
2) 1 mole of sulfhydryl modified epoxy compounds and 13 mole of triethylamine, 7 moles of epoxy soybean oil mixing are carried out heat cross-linking and react 14 h, temperature of reaction is 80 DEG C, puts into baking oven inside holding and dehydrates, obtain bio-rubber after curing molding.
Described multi-epoxy epoxy compounds is glyceryl three-glycidyl ester.Described single thiocarboxylic acid is selected from single sulfo-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 mixing solutions that dinethylformamide and methyl-sulphoxide form according to volume ratio 1:1, reaction times 18 h at 70 DEG C, carries out according to embodiment 1 linking agent that aftertreatment obtains containing many sulfydryls after completion of the reaction;
2) 1 mole of sulfhydryl modified epoxy compounds and 17 mole of triethylamine, 8 moles of epoxy soybean oil mixing are carried out heat cross-linking and react 17 h, temperature of reaction is 87 DEG C, puts into baking oven inside holding and dehydrates, obtain bio-rubber after curing molding.
Described multi-epoxy epoxy compounds comprises four Racemic glycidol diaminodiphenylmethane.Described single thiocarboxylic acid is single sulfo-n-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, stirring reaction 21 h at 50 DEG C, carries out according to embodiment 1 linking agent that aftertreatment obtains containing many sulfydryls after completion of the reaction;
2) 1 mole of sulfhydryl modified epoxy compounds and 7 mole of triethylamine, 4 moles of epoxy soybean oil mixing are carried out heat cross-linking and react 6 h, temperature of reaction is 100 DEG C, puts into baking oven inside holding and dehydrates, obtain bio-rubber after curing molding.
Described multi-epoxy epoxy compounds comprises bisphenol A type epoxy resin.Described single thiocarboxylic acid is single sulfo-n-caproic acid.Described initiator is triethyl-boron.
As shown in Figure 3, have the oxygen ester of strong polarity to exist on sulfydryl side, make sulfydryl polarity become large, active increase, ensure 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 tetrahydrofuran (THF) of 6L, stirring reaction 14 h at 39 DEG C, carries out according to embodiment 1 linking agent that aftertreatment obtains containing many sulfydryls after completion of the reaction;
2) 1 mole of sulfhydryl modified epoxy compounds and 15 mole of triethylamine, 7 moles of epoxy soybean oil mixing are carried out heat cross-linking and react 13 h, temperature of reaction is 60 DEG C, puts into baking oven inside holding and dehydrates, obtain bio-rubber after curing molding.
Described multi-epoxy epoxy compounds comprises bisphenol-s epoxy resin.Described single thiocarboxylic acid is single thioacetic 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 according to embodiment 1 linking agent that aftertreatment obtains containing many sulfydryls after completion of the reaction;
2) 1 mole of sulfhydryl modified epoxy compounds and 12 mole of triethylamine, 7 moles of epoxy soybean oil mixing are carried out heat cross-linking and react 23 h, temperature of reaction is 50 DEG C, puts into baking oven inside holding and dehydrates, obtain bio-rubber after curing molding.
Described multi-epoxy epoxy compounds is epoxy soybean oil.Described single thiocarboxylic acid is single sulfo-n-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-N,N-DIMETHYLACETAMIDE, at 30 DEG C, react 1 h, carry out according to embodiment 1 linking agent that aftertreatment obtains containing many sulfydryls after completion of the reaction;
2) 1 mole of sulfhydryl modified epoxy compounds and 0.01 molar part initiator, 0.1 mole of epoxy soybean oil mixing are carried out heat cross-linking reaction, put into baking oven inside holding after curing molding to dehydrate, obtain bio-rubber 1 h, temperature of reaction is 30 DEG C, put into baking oven inside holding after curing molding to dehydrate, obtain bio-rubber.
Described multi-epoxy epoxy compounds is 1,2,7,8-diepoxyoctane.Described single thiocarboxylic acid is selected from single thiobenzoic acid.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 mixing solutions that 15L is made up of according to volume ratio 2:1 chloroform and methylene dichloride, at 80 DEG C, react 24 h, carry out according to embodiment 1 linking agent that aftertreatment obtains containing many sulfydryls after completion of the reaction;
2) 1 mole of sulfhydryl modified epoxy compounds and 20 mole initiator, 10 moles of epoxy soybean oil mixing are carried out heat cross-linking and react 24 h, temperature of reaction is 100 DEG C, puts into baking oven inside holding and dehydrates, obtain bio-rubber after curing molding.
Described multi-epoxy epoxy compounds is 1，2-ethandiol diglycidylether.Described single thiocarboxylic acid is selected from single thioacetic 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 tetrahydrofuran (THF) of 6L, at 60 DEG C, react 12 h, carry out according to embodiment 1 linking agent that aftertreatment obtains containing many sulfydryls after completion of the reaction;
2) 1 mole of sulfhydryl modified epoxy compounds and 10 mole initiator, 5 moles of epoxy soybean oils mixing are carried out heat cross-linking, temperature of reaction is 60 DEG C, reaction times is 12 h, puts into baking oven inside holding and dehydrates, obtain bio-rubber after curing molding.
Described multi-epoxy epoxy compounds is BDDE.Described single thiocarboxylic acid is single sulfo-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 tetrahydrofuran (THF) of 10L, at 34 DEG C, react 2 h, carry out according to embodiment 1 linking agent that aftertreatment obtains containing many sulfydryls after completion of the reaction;
2) 1 mole of sulfhydryl modified epoxy compounds and 6 mole initiator, 0.6 mole of epoxy soybean oil mixing are carried out heat cross-linking reaction, temperature of reaction is 67 DEG C, reaction times is 2 h, puts into baking oven inside holding and dehydrates, obtain bio-rubber after curing molding.
Described multi-epoxy epoxy compounds comprises triglycidyl isocyanurate.Described single thiocarboxylic acid is single thio isobutyrate.Described initiator is peroxidation 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, stirring reaction 4 h at 42 DEG C, carries out according to embodiment 1 linking agent that aftertreatment obtains containing many sulfydryls after completion of the reaction;
2) 1 mole of sulfhydryl modified epoxy compounds and 8 mole initiator, 1.3 moles of epoxy soybean oils mixing are carried out heat cross-linking reaction, reaction 4h, temperature of reaction is 72 DEG C, puts into baking oven inside holding and dehydrates, obtain bio-rubber after curing molding.
Described multi-epoxy epoxy compounds is o-phthalic acid diglycidyl ester.Described single thiocarboxylic acid is single thiobenzoic acid.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, stirring reaction 14 h at 60 DEG C, carries out according to embodiment 1 linking agent that aftertreatment obtains containing many sulfydryls after completion of the reaction;
2) 1 mole of sulfhydryl modified epoxy compounds and 13 mole initiator, 7 moles of epoxy soybean oil mixing are carried out heat cross-linking and react 14 h, temperature of reaction is 80 DEG C, puts into baking oven inside holding and dehydrates, obtain bio-rubber after curing molding.
Described multi-epoxy epoxy compounds is glyceryl three-glycidyl ester.Described single thiocarboxylic acid is selected from single sulfo-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, stirring reaction 18 h at 70 DEG C, instead carries out according to embodiment 1 linking agent that aftertreatment obtains containing many sulfydryls after completion of the reaction;
2) 1 mole of sulfhydryl modified epoxy compounds and 17 mole initiator, 8 moles of epoxy soybean oil mixing are carried out heat cross-linking and react 17 h, temperature of reaction is 87 DEG C, puts into baking oven inside holding and dehydrates, obtain bio-rubber after curing molding.
Described multi-epoxy epoxy compounds comprises four Racemic glycidol diaminodiphenylmethane.Described single thiocarboxylic acid is single sulfo-n-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, stirring reaction 21 h at 50 DEG C, carries out according to embodiment 1 linking agent that aftertreatment obtains containing many sulfydryls after completion of the reaction;
2) 1 mole of sulfhydryl modified epoxy compounds and 7 mole initiator, 4 moles of epoxy soybean oil mixing are carried out heat cross-linking and react 6 h, temperature of reaction is 100 DEG C, puts into baking oven inside holding and dehydrates, obtain bio-rubber after curing molding.
Described multi-epoxy epoxy compounds comprises bisphenol A type epoxy resin.Described single thiocarboxylic acid is single sulfo-n-caproic acid.Described initiator is triethyl-boron.
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, stirring reaction 14 h at 39 DEG C, carries out according to embodiment 1 linking agent that aftertreatment obtains containing many sulfydryls after completion of the reaction;
2) 1 mole of sulfhydryl modified epoxy compounds and 15 mole initiator, 7 moles of epoxy soybean oil mixing are carried out heat cross-linking and react 13 h, temperature of reaction is 60 DEG C, puts into baking oven inside holding and dehydrates, obtain bio-rubber after curing molding.
Described multi-epoxy epoxy compounds comprises bisphenol-s epoxy resin.Described single thiocarboxylic acid is single thioacetic 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 according to embodiment 1 linking agent that aftertreatment obtains containing many sulfydryls after completion of the reaction;
2) 1 mole of sulfhydryl modified epoxy compounds and 12 mole initiator, 7 moles of epoxy soybean oil mixing are carried out heat cross-linking and react 23 h, temperature of reaction is 50 DEG C, puts into baking oven inside holding and dehydrates, obtain bio-rubber after curing molding.
Described multi-epoxy epoxy compounds is epoxy soybean oil.Described single thiocarboxylic acid is single sulfo-n-caprylic acid.Described initiator is BPO.
Embodiment 21
1) the triethylamine ring opening catalyst of the polyepoxy compound of 1 mole, 0.1 molar part, 1 molar part list thiocarboxylic acid are dissolved in the toluene of 3L; Stirring reaction 14h at 30 DEG C, carries out according to embodiment 1 linking agent that aftertreatment obtains containing many sulfydryls after completion of the reaction.
(2) 1 molar part is contained the linking agent of many sulfydryls, 0.20 molar part triethylamine, 10 molar part epoxy soybean oils, after mixing, at 100 DEG C of crosslinking reaction 14 h, put into baking oven inside holding after curing molding and dehydrate, obtain bio-rubber.
Described polyepoxy compound is 1,2,7,8-diepoxyoctane, 1，2-ethandiol diglycidylether, BDDE, triglycidyl isocyanurate.Its molar ratio is: 1:6:3:5.
Described single thiocarboxylic acid is by single thiobenzoic acid, single thioacetic acid, single sulfo-n Propanoic acid.Its molar ratio is: 1:3:4.
Described initiator is by BPO, AIBN, dialkyl, peroxidation two acyl.Its molar ratio is: 1:1:3:2.
Embodiment 22
1) the triethylamine ring opening catalyst of the polyepoxy compound of 1 mole, 0.1 molar part, 1 molar part list thiocarboxylic acid are dissolved in the tetrahydrofuran (THF) of 1L; Stirring reaction 1h at 30 DEG C, carries out according to embodiment 1 linking agent that aftertreatment obtains containing many sulfydryls after completion of the reaction.
(2) 1 molar part is contained the linking agent of many sulfydryls, 20 molar part triethylamines, 10 molar part epoxy soybean oils, after mixing, at 30 DEG C of crosslinking reaction 4 h, put into baking oven inside holding after curing molding and dehydrate, 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 is by single sulfo-n-caproic acid, single sulfo-n-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) the triethylamine ring opening catalyst of the polyepoxy compound of 1 mole, 0.3 molar part, 5 molar part list thiocarboxylic acids are dissolved in the tetrahydrofuran (THF) of 1L; React under agitation, temperature of reaction is 80 DEG C, and the reaction times is 4h, carries out the linking agent that aftertreatment obtains containing many sulfydryls after completion of the reaction according to embodiment 1.
(2) 1 molar part is contained the linking agent of many sulfydryls, 3 molar part triethylamines, 2 molar part epoxy soybean oils, after mixing, at 60 DEG C of crosslinking reaction 6 h, put into baking oven inside holding after curing molding and dehydrate, obtain bio-rubber.
Described polyepoxy compound is epoxypropyl chlorinated isocyanurates, o-phthalic acid diglycidyl ester.Its molar ratio is: 1:5.
Described single thiocarboxylic acid is single thioacetic acid, single sulfo-n Propanoic acid.Its molar ratio is 1:2.
Described initiator is by BPO, peroxidation two acyl.Its molar ratio is: 1:7.
Embodiment 24
1) the triethylamine ring opening catalyst of the polyepoxy compound of 1 mole, 3 molar part, 7 molar part list thiocarboxylic acids are dissolved in the tetrahydrofuran (THF) of 1L; React under agitation, temperature of reaction is 70 DEG C, and the reaction times is 13h, carries out the linking agent that aftertreatment obtains containing many sulfydryls after completion of the reaction according to embodiment 1.
(2) 1 molar part is contained the linking agent of many sulfydryls, 10 molar part triethylamines, 7 molar part epoxy soybean oils, after mixing, at 80 DEG C of crosslinking reaction 9 h, put into baking oven inside holding after curing molding and dehydrate, obtain bio-rubber.
Described polyepoxy compound is 1,2,7,8-diepoxyoctane, BDDE.Its molar ratio is: 1:3.
Described single thiocarboxylic acid is by single thioacetic acid, single sulfo-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 explaining and the present invention is described, instead of limits the invention, and in the protection domain of spirit of the present invention and claim, any amendment make the present invention and change, all fall into protection scope of the present invention.
Claims (4)
1. with soybean oil and epoxy soybean oil for a method for Material synthesis bio-rubber, it is characterized in that, its step is as follows:
(1) be dissolved in solvent by the triethylamine ring opening catalyst of the polyepoxy compound of 1 molar part, 0.1-20 molar part, 1-2 molar part list thiocarboxylic acid, the volumetric molar concentration of polyepoxy compound is 1 ~ 20mol/L; React under agitation, temperature of reaction is 30-80 DEG C, and the reaction times is 1-24h, removes triethylamine ring opening catalyst, solvent and excessive single thiocarboxylic acid after completion of the reaction, obtains the linking agent containing many sulfydryls; Described solvent is by methyl alcohol, ethanol, Virahol, toluene, benzene, chloroform, methylene dichloride, tetrahydrofuran (THF), diox, hexane, ether, ethyl acetate, N-Methyl pyrrolidone, N, one or more in dinethylformamide, N,N-dimethylacetamide, methyl-sulphoxide are according to any proportioning mixing composition;
(2) 1 molar part is contained the linking agent of many sulfydryls, 0.01-20 molar part triethylamine, 0.1-10 molar part epoxy soybean oil, after mixing, at 30-100 DEG C of crosslinking reaction 1-24 h, put into baking oven inside holding after curing molding and dehydrate, obtain bio-rubber; Or 1 molar part contained the linking agent of many sulfydryls, after 0.01-20 molar part initiator, 0.1-10 molar part soybean oil mix, at 30-100 DEG C of crosslinking reaction 1-24 h, put into baking oven inside holding after curing molding and dehydrate, obtain bio-rubber.
2. a kind of method that is Material synthesis bio-rubber with soybean oil and epoxy soybean oil according to claim 1, it is characterized in that, described polyepoxy compound is by 1, 2, 7, 8-diepoxyoctane, 1, 2-ethylene glycol diglycidylether, 1, 4-butanediol diglycidyl ether, triglycidyl isocyanurate, o-phthalic acid diglycidyl ester, glyceryl three-glycidyl ester or four Racemic glycidol diaminodiphenylmethane, bisphenol A type epoxy resin, bisphenol-s epoxy resin, epoxy-capped PDMS, one or more in epoxy soybean oil are according to any proportioning mixing composition.
3. a kind of method that is Material synthesis bio-rubber with soybean oil and epoxy soybean oil according to claim 1, it is characterized in that, described single thiocarboxylic acid is made up of according to any proportioning mixing one or more in single thiobenzoic acid, single thioacetic acid, single sulfo-n Propanoic acid, single thio isobutyrate, single sulfo-n-caproic acid, single sulfo-n-caprylic acid.
4. according to claim 1 a kind of take soybean oil as the method for Material synthesis bio-rubber, it is characterized in that, one or more during described initiator is as cuprous in triethyl aluminum, triethyl-boron or naphthoic acid by BPO, AIBN, dialkyl, peroxidation two acyl, tertiary amine, naphthenate, mercaptan, organometallic compound mix according to any proportioning and form.
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