CN102206341A - Soybean oil based elastomer raw rubber, soybean oil based elastomer and preparation method thereof - Google Patents
Soybean oil based elastomer raw rubber, soybean oil based elastomer and preparation method thereof Download PDFInfo
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- CN102206341A CN102206341A CN 201110094383 CN201110094383A CN102206341A CN 102206341 A CN102206341 A CN 102206341A CN 201110094383 CN201110094383 CN 201110094383 CN 201110094383 A CN201110094383 A CN 201110094383A CN 102206341 A CN102206341 A CN 102206341A
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Abstract
The invention relates to a soybean oil based elastomer and a preparation method thereof. An elastomer raw rubber is prepared by a ring-opening reaction of epoxy soybean oil and binary primary amines. The raw rubber and dicarboxylic acids or dicarboxylic anhydrides are mixed in an open mill, and the mixture is tabletted in a plate curometer to obtain the soybean oil based elastomer. The raw material used in the preparation method of the invention is mainly epoxy soybean oil; no introduction of catalysts or solvents is required during the reaction process; and the preparation method is environment-friendly.
Description
Technical field:
The present invention relates to soybean oil based elastomerics rubber, soybean oil based elastomerics and both preparation methods, belong to polymeric material field.
Background technology:
Rubber occupies important status in the national economic development, be a kind of strategic not replaceable goods and materials.In the world except natural rubber (account for rubber total amount 22%), remaining all is a synthetic rubber at present.Natural rubber is owing to be subjected to the restriction of physical environment, and its output is limited.Synthetic rubber substantially all obtains by the petroleum base monomer is synthetic, and along with the minimizing of petroleum resources, its cost will be more and more higher, and simultaneously, because petroleum-based products is non-renewable, and burning generates a large amount of CO
2, increase carbon emission, environment is polluted.Today paying attention to environmental protection, prepare bio-based elastomerics renewable, environmental protection and have very important significance.
In the last few years, people began to explore by organism-based raw material and prepared the polymkeric substance with mechanical property, and wherein plant oil is a kind of important material.Soybean oil is a present vegetable oil of output maximum in all vegetables oil, mainly is used as the softening agent of plastics or rubber by its epoxy soybean oil of obtaining of deriving.Epoxy soybean oil is obtained by the soybean oil epoxidation, and its structure centre is a glyceride structure, and three straight chains are arranged, and the carbon atom number is 16～18 on each chain, and 0～3 epoxy-functional is arranged on each chain.Utilize the epoxy-functional in the epoxy soybean oil to prepare the extensive attention that polymkeric substance has caused people, but it is considerably less to utilize the direct open loop of epoxy soybean oil to prepare the research of polymkeric substance at present.2004, Wool utilized epoxy soybean oil, polyacid, Viscotrol C, peroxide initiator etc., directly solidified to obtain a kind of elastic composite, mainly was used as flooring material, can replace the PVC material.But its tensile strength of material that obtains is substantially in 0～3MPa scope, and elongation at break does not reach 100% substantially.Its preparation method mainly is first with Viscotrol C and superoxide pre-polymerization, and with blend in container such as epoxy soybean oil, filler, linking agents, direct compression obtains, its raw material complexity, processing difficulties then.All be with rubber and reinforcing filler such as blend in mill such as carbon black, white carbon black in the general rubber processing, make fillers dispersed even by continuous shearing, thereby can obtain excellent mechanical property.Though the prepared elastic composite of Wool is also used epoxy soybean oil and polyprotonic acid and polyamine, its mechanism is to utilize polyprotonic acid or the polyamine linking agent as epoxy soybean oil.Because it is crosslinked that it directly carries out raw material, can't further process good blend, so its mechanics of materials intensity is lower, can't further improve with reinforcing fillers such as realization and carbon black, white carbon blacks, its application is very restricted.
Summary of the invention:
The purpose of this invention is to provide a kind of soybean oil based elastomerics rubber, soybean oil based elastomerics and both preparation methods, utilize epoxy soybean oil and binary primary amine ring-opening polymerization, obtain the elastomerics rubber earlier, utilize the esterification and crosslinking method to carry out the crosslinked soybean oil based elastomerics for preparing then.
A kind of soybean oil based elastomerics rubber of the present invention is made by epoxy soybean oil and binary primary amine ring-opening polymerization, and rubber is a kind of many branched structures, comprises ester functional group, hydroxy functional group and imine (see figure 1) in its structure.Its second-order transition temperature is between-40～10 ℃.Utilize the hydroxy functional group in the rubber, can carry out esterification and crosslinking to it with diprotic acid or dibasic acid anhydride.
The preparation method of described soybean oil based elastomerics rubber above the present invention is that 1: 2～1: 3 epoxy soybean oil and binary primary amine joins in the reactor with mol ratio, at N
2Under protection, the agitation condition, be heated to 100-160 ℃ and carry out ring-opening polymerization, take out behind the reaction 6-24h, oven dry obtains the elastomerics rubber;
The oxirane value of used epoxy soybean oil promptly has more than 3 epoxide groups in each epoxy soybean oil structure greater than 5.0.
Used binary primary amine is any in the following material or two or more mixture: quadrol, propylene diamine, butanediamine, pentamethylene diamine, hexanediamine, heptamethylene diamine, octamethylenediamine, nonamethylene diamine, decamethylene diamine, dodecane diamines, tridecane diamines, tetradecane diamines, Ursol D, new pentamethylene diamine.
The present invention also provides a kind of soybean oil based elastomerics, adopts above-mentioned soybean oil based elastomerics rubber and diprotic acid or dibasic acid anhydride esterification and crosslinking to obtain.Have only C, N, four kinds of elements of O, H in its structure, cross-linking set is an ester bond, makes it have the degradable performance.Elastomer crosslinked density be can change by the amount of adjusting linking agent diprotic acid or dibasic acid anhydride, thereby different glass transition temperature (10～30 ℃), tensile strength (1～20MPa) elastomerics prepared.
Above-mentioned method for producing elastomers, concrete steps and reaction conditions are:
With soybean oil based elastomerics rubber 100 mass parts and 2～30 mass parts diprotic acid or dibasic acid anhydrides, blend 10～50min in mill, compressing tablet on the compression molding instrument then, temperature is 150～190 ℃, the compressing tablet time is 10～90min, makes soybean oil based elastomerics.
Described diprotic acid is any in the following material or two or more mixture: oxalic acid, propanedioic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, dodecanedioic acid, undecane dicarboxylic acid, tetradecane diacid, terephthalic acid, new pentane diacid; Described dibasic acid anhydride is any in the following material or two or more mixture: Succinic anhydried, MALEIC ANHYDRIDE, Pyroglutaric acid, maleic anhydride or Tetra hydro Phthalic anhydride.
For improving performance such as elastomeric intensity, in the rubber mixing process, also can add strengthening agent, also can simultaneously or add other fillers separately elastomeric properties is carried out modification, the strengthening agent of adding can be carbon black, white carbon black etc.; Other fillers such as anti-aging agent etc.Its mixing process of rubber of the present invention's preparation is the same with the mixing process of common glue, all is to realize blend on two rollers.
The weight-average molecular weight of utilizing the multi-angle laser light scattering instrument to record the elastomerics rubber that the present invention prepares is 10～550,000.
The elastomerics rubber that the present invention prepares records second-order transition temperature by differential scanning calorimetric means and is-40～10 ℃, the cross-linked elastomer second-order transition temperature is-10～30 ℃, and recording elastomerics dissipation factor tan by the dynamic thermomechanometry means is 1～1.8.
Effect of the present invention: raw material of the present invention is epoxy soybean oil, and is renewable, do not rely on petroleum resources, therefore, has great importance for the deficient day by day problem that solves petroleum resources.
Therefore the elastomerics rubber that the present invention makes because that it does not take place is crosslinked, still can further be processed, and facilitates the introduction of nanoparticle and carries out reinforcement (comprising wild phases such as carbon black, white carbon black) and introduce other fillers strengthening its performance.Can be in mill and reinforcing filler, linking agent blend, compressing tablet is crosslinked on the compression molding instrument, obtains having the soybean oil based elastomerics of better performance.At first the elastomerics of the present invention's preparation belongs to polar rubber, therefore has the characteristics of general polar rubber, as has good oil-proofness; Secondly the elastomer rubber of the present invention's preparation is a saturated rubber, does not have the existence of two keys in the structure, therefore has good thermostability (Fig. 3); In addition, the pure glue of elastomer rubber of the present invention's preparation has higher mechanical property, and (tensile strength is 2～10MPa), therefore the pure glue of elastomerics has had certain using value, after reinforcement, its mechanical property improves a lot, tensile strength can reach 10～20Mpa, therefore, be hopeful to replace some rubber products commonly used, such as because its good oil-proofness, therefore can replace paracril is used for the automobile oil seat gasket, shore installation hose etc., again such as having higher dissipation factor (1.5～1.8) and suitable damping temperature domain (10～50 ℃) owing to its pure glue, therefore can make the bike vibration isolating pad with in daily life, vibration-proof pads and sound insulation earplug etc.
Elastomerics of the present invention utilizes hydroxyl in the rubber and diprotic acid or dibasic acid anhydride to carry out esterification and crosslinking, obtain a kind of polyester elastomer, its cross-linking set is an ester bond, glyceryl ester group owing to the epoxy soybean oil center decomposes easily simultaneously, therefore the elastomerics of the present invention's preparation is biodegradable, because pure glue has had certain mechanical property, therefore has the potential using value in field of medical materials.
In addition, in the method for producing elastomers of the present invention, if utilize the binary primary amine reaction of epoxy soybean oil and bio-based to obtain rubber, utilize bio-based diprotic acid or dibasic acid anhydride to carry out esterification and crosslinking then, just can obtain full bio-based elastomerics, and in the whole process of preparation and the introducing of catalyst-free or solvent, the real bio-based elastomerics of realizing on the complete meaning, do not rely on petroleum resources, along with the rising of petroleum resources price, its cost will have very large advantage with respect to petroleum base rubber.Environment is not polluted, and degradable had very important significance in today of paying attention to environmental protection.
Description of drawings:
Fig. 1 the present invention prepares elastomerics rubber reactive group reason synoptic diagram (embodiment 1), can confirm by the nuclear magnetic spectrogram of Fig. 2.
The elastomerics rubber nuclear magnetic spectrogram that Fig. 2 embodiment of the invention 1 prepares
The elastomerics thermogravimetric curve that Fig. 3 embodiment of the invention 2 prepares
Fig. 2 is the nuclear magnetic spectrogram of the elastomerics rubber for preparing of embodiment 1.As can be seen, represent 2.89～3.11ppm peak of the hydrogen characteristic peak on the epoxide group to disappear among the figure, the hydrogen characteristic peak in the representation hydroxy functional group at 3.23ppm place occurred, prove that ring-opening reaction has taken place for decamethylene diamine and epoxide group, react complete substantially.
Embodiment:
Embodiment 1: the elastomeric preparation of epoxy soybean oil-decamethylene diamine-Succinic anhydried
Epoxy soybean oil (oxirane value is 6.0, down together) 100g and 36g decamethylene diamine are joined in the there-necked flask, be heated to 120 ℃, logical N
2Protection, agitation condition reacted 8 hours down, took out, and oven dry is 5 hours in 60 ℃ of vacuum drying ovens, obtains required rubber.Utilizing the multi-angle laser light scattering instrument to record its weight-average molecular weight is 16.5 ten thousand, utilizes differential scanning calorimetric means to record its second-order transition temperature and is-18 ℃.
The blend 15min in mill with above-mentioned rubber 100g and 7g Succinic anhydried places compressing tablet on the compression molding instrument then, and temperature is 160 ℃, and the compressing tablet time is 70min, obtains required elastomerics.
Embodiment 2: the elastomeric preparation of epoxy soybean oil-butanediamine-sebacic acid
Epoxy soybean oil 100g and 16g butanediamine are joined in the there-necked flask, be heated to 120 ℃, logical N
2Protection, agitation condition reacted 6 hours down, took out, and oven dry is 5 hours in 60 ℃ of vacuum drying ovens, obtains required rubber.Utilizing the multi-angle laser light scattering instrument to record its weight-average molecular weight is 18.5 ten thousand, utilizes differential scanning calorimetric means to record its second-order transition temperature and is-15 ℃.
With above-mentioned rubber 100g and 11g sebacic acid, 60g carbon black (N550) blend 25min in mill, place compressing tablet on the compression molding instrument then, temperature is 170 ℃, the compressing tablet time is 40min, obtains required elastomerics.
Embodiment 3: the epoxy soybean oil-elastomeric preparation of tetradecane diamines-maleic anhydride
Epoxy soybean oil 100g and 40g tetradecane diamines are joined in the there-necked flask, be heated to 120 ℃, logical N
2Protection, agitation condition reacted 18 hours down, took out, and oven dry is 5 hours in 60 ℃ of vacuum drying ovens, obtains required rubber.Utilizing the multi-angle laser light scattering instrument to record its weight-average molecular weight is 7.8 ten thousand, utilizes differential scanning calorimetric means to record its second-order transition temperature and is-28 ℃.
With above-mentioned rubber 100g and 9g maleic anhydride, 60g white carbon black (DM10) blend 25min in mill, place compressing tablet on the compression molding instrument then, temperature is 180 ℃, the compressing tablet time is 30min, obtains required elastomerics.
Embodiment 4: the elastomeric preparation of epoxy soybean oil-butanediamine-Succinic anhydried
With the rubber 100g of embodiment 2 preparation and 9g Succinic anhydried, 60g carbon black (N330) blend 25min in mill, place compressing tablet on the compression molding instrument then, temperature is 160 ℃, the compressing tablet time is 30min, obtains required elastomerics.
Embodiment 5: epoxy soybean oil-Ursol D-face elastomeric preparation of phthalate anhydride
Epoxy soybean oil 100g and 30g Ursol D are joined in the there-necked flask, be heated to 160 ℃, logical N
2Protection, agitation condition reacted 3 hours down, took out, and oven dry is 5 hours in 60 ℃ of vacuum drying ovens, obtains required rubber.Utilizing the multi-angle laser light scattering instrument to record its weight-average molecular weight is 29.8 ten thousand, utilizes differential scanning calorimetric means to record its second-order transition temperature and is-8 ℃.
Above-mentioned rubber 100g and 15g are faced phthalate anhydride, 40g carbon black (N234) blend 25min in mill, place compressing tablet on the compression molding instrument then, temperature is 190 ℃, and the compressing tablet time is 16min, obtains required elastomerics.
The elastomer performance table that table 1 the present invention prepares
| Used | Embodiment | 1 | |
|
|
|
|
| Tg(℃)/DSC | 2 | -10 | -10 | -6 | 10 | ||
| Tensile strength (MPa) | GB/T?528 | 5.8 | 13.8 | 11.2 | 12.3 | 18.8 | |
| Elongation at break (%) | GB/T?528 | 220 | 180 | 280 | 160 | 130 | |
| Shao A hardness (degree) | GB/T?6031 | 35 | 45 | 42 | 49 | 55 |
Claims (7)
1. a soybean oil based elastomerics rubber is made by epoxy soybean oil and binary primary amine ring-opening polymerization.
2. the preparation method of the described soybean oil based elastomerics rubber of claim 1 is that 1: 2～1: 3 epoxy soybean oil and binary primary amine joins in the reactor with mol ratio, at N
2Under protection, the agitation condition, be heated to 100-160 ℃ and carry out ring-opening polymerization, take out behind the reaction 6-24h, oven dry obtains the elastomerics rubber;
The oxirane value of used epoxy soybean oil is greater than 5.0.
3. according to the preparation method of the described rubber of claim 2, it is characterized in that: described binary primary amine is any in the following material or two or more mixture: quadrol, propylene diamine, butanediamine, pentamethylene diamine, hexanediamine, heptamethylene diamine, octamethylenediamine, nonamethylene diamine, decamethylene diamine, dodecane diamines, tridecane diamines, tetradecane diamines, Ursol D, new pentamethylene diamine.
4. a soybean oil based elastomerics adopts described rubber of claim 1 and diprotic acid or dibasic acid anhydride to obtain through esterification and crosslinking.
5. described method for producing elastomers of claim 4, concrete steps and reaction conditions are: with described rubber 100 mass parts of claim 1 and 2～30 mass parts diprotic acid or dibasic acid anhydrides, blend 10～50min in mill, compressing tablet on the compression molding instrument then, temperature is 150～190 ℃, the compressing tablet time is 10～90min, makes soybean oil based elastomerics.
6. according to the described method for producing elastomers of claim 5, it is characterized in that: described diprotic acid is any in the following material or two or more mixture: oxalic acid, propanedioic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, dodecanedioic acid, undecane dicarboxylic acid, tetradecane diacid, terephthalic acid, new pentane diacid; Described dibasic acid anhydride is any in the following material or two or more mixture: Succinic anhydried, MALEIC ANHYDRIDE, Pyroglutaric acid, maleic anhydride or Tetra hydro Phthalic anhydride.
7. according to the described method for producing elastomers of claim 5, it is characterized in that: add an amount of strengthening agent or other fillers in the rubber mixing process or together add other fillers with strengthening agent.
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| CN201110094383XA CN102206341B (en) | 2011-04-15 | 2011-04-15 | Soybean oil based elastomer raw rubber, soybean oil based elastomer and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104592487A (en) * | 2015-01-12 | 2015-05-06 | 浙江碳谷上希材料科技有限公司 | Method for synthesizing biological base rubber by using soybean oil and epoxidized soybean oil as raw materials |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60168718A (en) * | 1984-02-13 | 1985-09-02 | Nitto Electric Ind Co Ltd | Underwater-applicable epoxy resin composition |
| CN1052893A (en) * | 1990-11-12 | 1991-07-10 | 天津大学 | Enhanced moisture-resistant agent for resin bonded sand |
-
2011
- 2011-04-15 CN CN201110094383XA patent/CN102206341B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60168718A (en) * | 1984-02-13 | 1985-09-02 | Nitto Electric Ind Co Ltd | Underwater-applicable epoxy resin composition |
| CN1052893A (en) * | 1990-11-12 | 1991-07-10 | 天津大学 | Enhanced moisture-resistant agent for resin bonded sand |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104592487A (en) * | 2015-01-12 | 2015-05-06 | 浙江碳谷上希材料科技有限公司 | Method for synthesizing biological base rubber by using soybean oil and epoxidized soybean oil as raw materials |
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| CN102206341B (en) | 2012-07-04 |
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