CN101481471B - Raw materials formula for producing single-shell sulfur microcapsule - Google Patents
Raw materials formula for producing single-shell sulfur microcapsule Download PDFInfo
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- CN101481471B CN101481471B CN2009100090774A CN200910009077A CN101481471B CN 101481471 B CN101481471 B CN 101481471B CN 2009100090774 A CN2009100090774 A CN 2009100090774A CN 200910009077 A CN200910009077 A CN 200910009077A CN 101481471 B CN101481471 B CN 101481471B
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Abstract
The invention discloses a raw material formulation for manufacturing single lamella sulfur microcapsules, which comprises sublimed sulfur, toluene di-isocyanate, water, quadrol and diethylenetriamine. The single lamella sulfur microcapsule is prepared with the formulation by an interface polymerization method, gives off sulfur under a certain temperature and plays a role in sulfuration. The single lamella sulfur microcapsule, the mass fraction of the sulfur of which ranges from 5-53%, can be prepared by changing the matching of the raw materials.
Description
Technical field
The invention belongs to a kind of composition of raw materials for preparing single-shell sulfur microcapsule.
Background technology
Vulcanizing agent is claimed linking agent again, in sulfidation can with rubber generation chemical action.Through the connection of one or more sulphur atoms, form crosslinked reticulated structure between the rubber molecule, performances such as its elasticity, hardness, stretching all are greatly improved.
Sulphur is the vulcanizing agent that is applied to rubber the earliest, and it is not only cheap, and the elasticity of cross-linked rubber and fatigue performance are good.But the solubility with temperature of sulphur in rubber raises and increases, and therefore when its addition was big, rubber unvulcanizate cools off rear section sulphur will separate out on the sizing material surface with crystallized form, causes " bloom "." bloom " not only influences the outward appearance of rubber item, also can reduce its surface adhesion, makes course of processing difficulty increases such as adhesion-molded.In order to reduce " bloom ", should select the bigger vulcanizing agent of relative molecular mass for use, sulphur just is difficult to migration from sizing material, separates out like this.Prevent that " bloom " has two approach: 1. select the bigger sulphur of relative molecular mass for use, i.e. insoluble sulfur; 2. coat one deck polymer or small molecules film on common sulphur surface, make itself and sizing material have good consistency, and take into account the thermostability and the chemicalstability of sulphur, improved the performance of rubber item.
Insoluble sulfur has unreactiveness and physics inertia, when being used for the vulcanization of rubber, and difficult the migration, thereby can make vulcanized rubber tackify, not " bloom ", and reduce incipient scorch and prolong the sizing material shelf-time, be most widely used in the world at present vulcanizer.Insoluble sulfur has been widely used in carcass sizing material, buffering sizing material at present as vulcanizing agent and vulcanization accelerator, is fit to make tire, sebific duct, travelling belt, automobile rubber spare, rubber roll, rubber overshoes and latex product etc.
But the insoluble sulfur cost is very high, is about 5～10 times of common sulphur, so it can not substitute common sulphur all the time fully, and the conventional production methods of insoluble sulfur is to leach the content that improves insoluble sulfur with dithiocarbonic anhydride.There are shortcomings such as energy consumption is big, equipment corrosion is serious, inflammable and explosive in this method; And the product stability of producing is poor, is easy to depolymerization and is reduced into common soluble sulfur.
Sulfur microcapsule is to coat one deck polymer or small molecules film on common sulphur surface.Because the diameter of microcapsule is bigger, therefore be difficult to migration from sizing material, separate out, can prevent rubber " bloom ".Adopting interfacial polymerization to prepare that sulfur microcapsule technology is simple, efficient, cost is low, with respect to Manufacture of insoluble sulphur technology Environmental Safety, is a kind of vulcanizer of developing.
Summary of the invention
The present invention proposes a kind of composition of raw materials of manufacture order shell sulfur microcapsule, it is made up of sublimed sulphur, tolylene diisocyanate, water, quadrol, diethylenetriamine etc.This prescription is prepared single-shell sulfur microcapsule through interfacial polymerization, and fusing at a certain temperature discharges sulphur, can play the effect of the vulcanization of rubber.The present invention can prepare the single-shell sulfur microcapsule of the massfraction of sulphur in 5～63% scopes through changing proportion of raw materials.
A kind of composition of raw materials of manufacture order shell sulfur microcapsule, the ratio of weight and number of its each component is:
Sublimed sulphur 0.55～9.4
Tolylene diisocyanate 4～6.5
OP emulsifying agent 0.2～0.5
Gelatin or Z 150PH 1.5
Water 63.5
Formic acid 0.5～1
Quadrol 0.5～2
Diethylenetriamine 1～3
The object of the present invention is to provide a kind of single-shell sulfur microcapsule preparing method's of cheap and easy to get, Environmental Safety composition of raw materials.The sulfur microcapsule that adopts this formulation to go out is a kind of powdery substance of almost spherical, can prepare the sulfur microcapsule of massfraction in 5～63% scopes of sulphur, and diameter is in 0.2～4 mu m range.This product adds in the rubber, is difficult to migration from sizing material, separates out, and can prevent " bloom " phenomenon of sizing material effectively.Compared to insoluble sulfur, simple, the Environmental Safety, with low cost of the single-shell sulfur microcapsule preparation technology who adopts this formulation to go out can be used as vulcanizer.
Embodiment
Embodiment 1
The quality of each component of preparation single-shell sulfur microcapsule is following:
Sublimed sulphur 0.55g
Tolylene diisocyanate 6.5g
OP emulsifying agent 0.4g
Z 150PH 1.5g
Water 63.5g
Diethylenetriamine 3g
Quadrol 1.5g
Formic acid 0.8g
The preparation method of single-shell sulfur microcapsule is following:
(1) polyvinyl alcohol water solution of preparation 15g 10% adds 0.4g OP emulsifying agent again, and heated and stirred is prepared water;
(2) 0.55g sublimed sulphur and 6.5g tolylene diisocyanate are poured in the beaker, stirred 2min, prepare oil phase;
(3) oil phase is slowly joined aqueous phase, with 15000rpm rotating speed stirring and emulsifying 10min, obtain emulsion, emulsion is transferred in the four-hole boiling flask with FM200 laboratory high speed shear mulser;
(4) the logical condensing reflux water device of going up contains the aqueous solution of 1.5g quadrol and 3g diethylenetriamine with constant pressure funnel Dropwise 5 4.5g in four-hole boiling flask, and the control rate of addition is 0.3mL/min; Adding 0.8g formic acid transfers to 3 with the pH value of solution, and stirring velocity is 1200rpm, and temperature is controlled at 55 ℃, reacts 6 hours;
(5) reduce to room temperature, suction filtration, washing, vacuum-drying or spraying drying are mixed stirring with trichloromethane and sulfur microcapsule, the sulphur that does not superscribe on the flush away microcapsule shell wall, and vacuum-drying again can obtain 9.8g single-shell sulfur microcapsule product.
Single-shell sulfur microcapsule of the present invention is used sem observation, and the product diameter is in 0.2～1.2 mu m range, and the massfraction of sulphur is 4.9%.
Embodiment 2
The quality of each component of preparation single-shell sulfur microcapsule is following:
Sublimed sulphur 1.5g
Tolylene diisocyanate 5.5g
OP emulsifying agent 0.3g
Gelatin 1.5g
Water 63.5g
Diethylenetriamine 3g
Quadrol 0.5g
Formic acid 0.6g
The preparation method of single-shell sulfur microcapsule is following:
(1) aqueous gelatin solution of preparation 15g 10% adds 0.3g OP emulsifying agent again, and heated and stirred is prepared water;
(2) 1.5g sublimed sulphur and 5.5g tolylene diisocyanate are poured in the beaker, stirred 2min, prepare oil phase;
(3) oil phase is slowly joined aqueous phase, with 15000rpm rotating speed stirring and emulsifying 10min, obtain emulsion, emulsion is transferred in the four-hole boiling flask with FM200 laboratory high speed shear mulser;
(4) the logical condensing reflux water device of going up contains the aqueous solution of 0.5g quadrol, 3g diethylenetriamine with constant pressure funnel Dropwise 5 3.5g in four-hole boiling flask, and the control rate of addition is 0.3mL/min; Adding 0.6g formic acid transfers to 3 with the pH value of solution, and stirring velocity is 1200rpm, and temperature is controlled at 55 ℃, reacts 6 hours;
(5) reduce to room temperature, suction filtration, washing, vacuum-drying or spraying drying are mixed stirring with trichloromethane and sulfur microcapsule, the sulphur that does not superscribe on the flush away microcapsule shell wall, and vacuum-drying again can obtain 8.8g sulfur microcapsule product.
Single-shell sulfur microcapsule of the present invention is used sem observation, and the product diameter is in 0.2～1.6 mu m range, and the massfraction of sulphur is 14.8%.
Embodiment 3
The quality of each component of preparation single-shell sulfur microcapsule is following:
Sublimed sulphur 3.3g
Tolylene diisocyanate 4.5g
OP emulsifying agent 0.2g
Gelatin 1.5g
Water 63.5g
Diethylenetriamine 1.5g
Quadrol 1.5g
Formic acid 0.5g
The preparation method of single-shell sulfur microcapsule is following:
(1) aqueous gelatin solution of preparation 15g 10% adds 0.2g OP emulsifying agent again, and heated and stirred is prepared water;
(2) 3.3g sublimed sulphur and 4.5g tolylene diisocyanate are poured in the beaker, stirred 2min, prepare oil phase;
(3) oil phase is slowly joined aqueous phase, with 11000rpm rotating speed stirring and emulsifying 10min, obtain emulsion, emulsion is transferred in the four-hole boiling flask with FM200 laboratory high speed shear mulser;
(4) the logical condensing reflux water device of going up contains the aqueous solution of 1.5g quadrol and 1.5g diethylenetriamine with constant pressure funnel Dropwise 5 3g in four-hole boiling flask, and the control rate of addition is 0.3mL/min; Adding 0.5g formic acid transfers to 4 with the pH value of solution, and stirring velocity is 800rpm, and temperature is controlled at 55 ℃, reacts 6 hours;
(5) reduce to room temperature, suction filtration, washing, vacuum-drying or spraying drying are mixed stirring with trichloromethane and sulfur microcapsule, the sulphur that does not superscribe on the flush away microcapsule cyst wall, and vacuum-drying again can obtain 9.2g single-shell sulfur microcapsule product.
Single-shell sulfur microcapsule of the present invention is used sem observation, and the product diameter is in 0.7～3.3 mu m range, and the massfraction of sulphur is 32.5%.
Embodiment 4
The quality of each component of preparation single-shell sulfur microcapsule is following:
Sublimed sulphur 5.4g
Tolylene diisocyanate 6g
OP emulsifying agent 0.2g
Gelatin 1.5g
Water 63.5g
Diethylenetriamine 2g
Quadrol 2g
Formic acid 1g
The preparation method of single-shell sulfur microcapsule is following:
(1) aqueous gelatin solution of preparation 15g 10% adds 0.2g OP emulsifying agent again, and heated and stirred is prepared water;
(2) 5.4g sublimed sulphur and 6g tolylene diisocyanate are poured in the beaker, stirred 2min, prepare oil phase;
(3) oil phase is slowly joined aqueous phase, with 12000rpm rotating speed stirring and emulsifying 10min, obtain emulsion, emulsion is transferred in the four-hole boiling flask with FM200 laboratory high speed shear mulser;
(4) the logical condensing reflux water device of going up contains the aqueous solution of 2g quadrol and 2g ethene triamine with constant pressure funnel Dropwise 5 4g in four-hole boiling flask, and the control rate of addition is 0.2mL/min; Adding 1g formic acid transfers to 3.5 with the pH value of solution, and stirring velocity is 1000rpm, and temperature is controlled at 55 ℃, reacts 6 hours;
(5) reduce to room temperature, suction filtration, washing, vacuum-drying or spraying drying are mixed stirring with trichloromethane and sulfur microcapsule, the sulphur that does not superscribe on the flush away microcapsule shell wall, and vacuum-drying again can obtain 13.5g single-shell sulfur microcapsule product.
Single-shell sulfur microcapsule of the present invention is used sem observation, and the product diameter is in 0.7～2.8 mu m range, and the massfraction of sulphur is 37.0%.
Embodiment 5
The quality of each component of preparation single-shell sulfur microcapsule is following:
Sublimed sulphur 5.8g
Tolylene diisocyanate 5g
OP emulsifying agent 0.2g
Z 150PH 1.5g
Water 63.5g
Diethylenetriamine 2g
Quadrol 1g
Formic acid 1g
The preparation method of single-shell sulfur microcapsule is following:
(1) polyvinyl alcohol water solution of preparation 15g 10% adds 0.2g OP emulsifying agent again, and heated and stirred is prepared water;
(2) 5.8g sublimed sulphur and 5g tolylene diisocyanate are poured in the beaker, stirred 2min, prepare oil phase;
(3) oil phase is slowly joined aqueous phase, with 10000rpm rotating speed stirring and emulsifying 10min, obtain emulsion, emulsion is transferred in the four-hole boiling flask with FM200 laboratory high speed shear mulser;
(4) the logical condensing reflux water device of going up contains the aqueous solution of 1g quadrol and 2g diethylenetriamine with constant pressure funnel Dropwise 5 3g in four-hole boiling flask, and the control rate of addition is 0.2mL/min; Adding 1g formic acid transfers to 4 with the pH value of solution, and stirring velocity is 750rpm, and temperature is controlled at 55 ℃, reacts 6 hours;
(5) reduce to room temperature, suction filtration, washing, vacuum-drying or spraying drying are mixed stirring with trichloromethane and sulfur microcapsule, the sulphur that does not superscribe on the flush away microcapsule cyst wall, and vacuum-drying again can obtain 11.9g single-shell sulfur microcapsule product.
Single-shell sulfur microcapsule of the present invention is used sem observation, and the product diameter is in 1～4 mu m range, and the massfraction of sulphur is 46.2%.
Embodiment 6
The quality of each component of preparation single-shell sulfur microcapsule is following:
Sublimed sulphur 9.4g
Tolylene diisocyanate 4g
OP emulsifying agent 0.5g
Z 150PH 1.5g
Water 63.5g
Diethylenetriamine 2g
Quadrol 1g
Formic acid 0.8g
The preparation method of single-shell sulfur microcapsule is following:
(1) polyvinyl alcohol water solution of preparation 15g 10% adds 0.5g OP emulsifying agent again, and heated and stirred is prepared water;
(2) 9.4g sublimed sulphur and 4g tolylene diisocyanate are poured in the beaker, stirred 2min, prepare oil phase;
(3) oil phase is slowly joined aqueous phase, with 15000rpm rotating speed stirring and emulsifying 10min, obtain emulsion, emulsion is transferred in the four-hole boiling flask with FM200 laboratory high speed shear mulser;
(4) the logical condensing reflux water device of going up contains the aqueous solution of 1g quadrol and 2g diethylenetriamine with constant pressure funnel Dropwise 5 3g in four-hole boiling flask, and the control rate of addition is 0.3mL/min; Adding 0.8g formic acid transfers to 3 with the pH value of solution, and stirring velocity is 1200rpm, and temperature is controlled at 55 ℃, reacts 6 hours;
(5) reduce to room temperature, suction filtration, washing, vacuum-drying or spraying drying are mixed stirring with trichloromethane and sulfur microcapsule, the sulphur that does not superscribe on the flush away microcapsule shell wall, and vacuum-drying again can obtain 14.6g single-shell sulfur microcapsule product.
Single-shell sulfur microcapsule of the present invention is used sem observation, and the product diameter is in 0.2～1.3 mu m range, and the massfraction of sulphur is 62.7%.
Claims (1)
1. single-shell sulfur microcapsule, it is characterized in that: it is processed by following component, and the ratio of weight and number of its each component is:
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| CN2009100090774A CN101481471B (en) | 2009-02-17 | 2009-02-17 | Raw materials formula for producing single-shell sulfur microcapsule |
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| CN2009100090774A CN101481471B (en) | 2009-02-17 | 2009-02-17 | Raw materials formula for producing single-shell sulfur microcapsule |
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| CN101481471B true CN101481471B (en) | 2012-11-14 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101671421B (en) * | 2009-10-21 | 2012-05-23 | 中国石油大学(北京) | Raw material formula for producing sulfur microcapsules using melamine resins |
| CN111073054B (en) * | 2019-12-04 | 2021-11-09 | 江苏卡欧化工股份有限公司 | Anti-slippery resin-based multifunctional rubber vulcanization accelerator and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1730525A (en) * | 2005-08-16 | 2006-02-08 | 上海工程技术大学 | Microcapsulized expansion type flame-proof rubber and its preparation method |
| EP1536883B1 (en) * | 2002-09-10 | 2007-03-28 | Schill & Seilacher AG | Microcapsules used for producing rubber and method for their production |
| CN101263192A (en) * | 2005-07-28 | 2008-09-10 | 希尔和塞拉彻股份有限公司 | Microencapsulated rubber additives and method for the production thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1536883B1 (en) * | 2002-09-10 | 2007-03-28 | Schill & Seilacher AG | Microcapsules used for producing rubber and method for their production |
| CN101263192A (en) * | 2005-07-28 | 2008-09-10 | 希尔和塞拉彻股份有限公司 | Microencapsulated rubber additives and method for the production thereof |
| CN1730525A (en) * | 2005-08-16 | 2006-02-08 | 上海工程技术大学 | Microcapsulized expansion type flame-proof rubber and its preparation method |
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