CN101475730A - Preparation of bilaminar membrane sulfur microcapsule - Google Patents
Preparation of bilaminar membrane sulfur microcapsule Download PDFInfo
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- CN101475730A CN101475730A CNA2009100051093A CN200910005109A CN101475730A CN 101475730 A CN101475730 A CN 101475730A CN A2009100051093 A CNA2009100051093 A CN A2009100051093A CN 200910005109 A CN200910005109 A CN 200910005109A CN 101475730 A CN101475730 A CN 101475730A
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Abstract
The invention discloses a method for preparing a double layer coating sulfur microcapsule. The method takes sulfur as a core material, and a double lamella polymer material as a wall material to prepare the double layer coating sulfur microcapsule by an interfacial polymerization method. Compared with a single lamella microcapsule, the double layer coating sulfur microcapsule improves the compactness of a coating core material. The method can adjust speed of the microcapsule releasing sulfur through changing the average diameter and the lamella thickness of the microcapsule so as to achieve the requirement of practical application. The sulfur microcapsule has less pollution to the environment, and has the advantages of simple process, safe operation and low cost, thereby being a rubber vulcanizing agent with development value.
Description
Technical field
The invention belongs to a kind of preparation method who can be used as the sulfur microcapsule of vulcanizer, particularly a kind of preparation method of bilaminar membrane sulfur microcapsule.
Background technology
Insoluble sulfur is still a kind of most important vulcanizing agent at present, but the Manufacture of insoluble sulphur method is to adopt dithiocarbonic anhydride to leach the content that improves the product insoluble sulfur.There are shortcomings such as energy consumption is big, equipment corrosion is serious in this method; Dithiocarbonic anhydride is inflammable, explosive simultaneously, toxicity is big, makes production operation very dangerous.In addition, the price of insoluble sulfur is very expensive, and is difficult to be dispersed in the rubber stock, and when it is in statu quo stored or is stored in the rubber stock instability, can become the solubility crystallized form.Sulfur microcapsule can well be avoided above problem.
Sulfur microcapsule is to coat one deck polymer or small molecules film on common sulphur surface, forms the microcapsule that coat sulphur.
Microcapsule are by miniature vessel natural or that synthetic macromolecule is made, and it is that solid, liquid or gas are wrapped in the small capsule, and its shape can be sphere, kidney type, grain shape or bulk etc.The material that forms microcapsule can be avoided the influence of environment, thereby keep its stability owing to isolated with external environment; And under suitable condition, encapsulated material can discharge again.Microcapsule are made up of encapsulated material and coating material, are wrapped in inner material and are commonly referred to as core, and coating material is called the shell material.The diameter range of microcapsule is very wide, can be from nano level to the millimeter level.
The purpose of microcapsule mainly contain following some: the physical properties of improving material; Controlling slow release; The protective core material is avoided environmental influence; Reduce health hazard, reduce toxic side effect; Shielding taste and smell; The smell sustained release; Be used for the separation of the Incompatible Substance of specific purposes.
Microcapsule can adopt the interfacial polymerization preparation.Interfacial polymerization is a kind of novel microcapsule coating technology.Its principle is that two kinds of monomers that have the different activities group are dissolved in respectively in the immiscible solvent, and when a kind of solution was dispersed in the another kind of solution, the interface of two kinds of solution can form polymeric film.
Sulfur microcapsule and sizing material have good consistency, can take into account the thermostability and the chemical stability of sulphur, improve the performance of rubber item.When reach certain temperature when above the coating layer fusing discharge sulphur, and do not influence the sulfuration of sulphur in rubber.Coating layer after the fusing can not exert an influence to the physics and the chemical property of rubber, and the performances such as ageing-resistant and anti-incipient scorch of rubber are made moderate progress, and sulfur microcapsule is a kind of vulcanizer with DEVELOPMENT PROSPECT.
Summary of the invention
The present invention proposes a kind of preparation method of bilaminar membrane sulfur microcapsule, coat last layer urea-formaldehyde resin polymeric membrane, improved the compactness of parcel core on the surface of single-shell sulfur microcapsule.The bivalve layer that the cyst material of bilaminar membrane sulfur microcapsule is made up of polyureas and two kinds of materials of urea-formaldehyde resin.
The preparation method of bilaminar membrane sulfur microcapsule is as follows:
(1) formalin with urea and 37% mixes, pouring in the four-hole boiling flask that condenser is housed, with trolamine the pH value of solution is transferred to 9, is that 50 ℃, stirring velocity are under 1050～1500rpm condition in temperature then, reacted 2 hours, and prepared urea aldehyde performed polymer;
(2) sulphur and tolylene diisocyanate are poured in the beaker, stirred 5min, prepare oil phase; Emulsifying agent is added in the aqueous gelatin solution, prepare water; Oil phase is slowly joined aqueous phase, and high-speed stirring 10min forms emulsion, and emulsion is transferred in the four-hole boiling flask;
(3) in four-hole boiling flask, drip the aqueous solution that contains quadrol and diethylenetriamine with constant pressure funnel, after dripping, stirred 2 hours;
(4) the urea aldehyde performed polymer for preparing is added in the four-hole boiling flask, adds formic acid, the pH value of regulator solution is 4, is that 60～75 ℃, stirring velocity are to react 8 hours under the condition of 750～1200rpm in temperature;
(5) pour out reaction solution, wait drop to room temperature after, suction filtration, washing, it is dry to put into baking oven, again organic solvent and product is mixed stirring, the sulphur that coats on the flush away microcapsule shell wall, it is dry to continue to put into baking oven, can obtain the bilaminar membrane sulfur microcapsule product.
Technology of the present invention is simple, operational safety, and prepared sulfur microcapsule is a kind of lurid powder, can prepare the sulfur microcapsule of sulphur massfraction in 25～53% scopes, and the particle diameter scope is between 0.5～7 μ m.Compared to common sulphur, this product diameter is bigger, adds in the rubber, is difficult to migration from sizing material, separates out, and can prevent effectively that " bloom " phenomenon of sizing material from occurring.In addition, problem such as that this invention has solved that insoluble sulfur production exists is inflammable, explosive, toxicity is big is a kind of vulcanizer that exploitation is worth that has.
Embodiment
Embodiment 1
The quality of each component of preparation bilaminar membrane sulfur microcapsule is as follows:
Sublimed sulphur 3g
Urea 2.5g
37% formaldehyde solution 5g
Trolamine 0.2g
Tween?61 0.5g
Gelatin 2g
Tolylene diisocyanate 3.6g
Water 70g
Formic acid 0.3g
Diethylenetriamine 1g
Quadrol 1g
The preparation method of bilaminar membrane sulfur microcapsule is as follows:
(1) formalin with 2.5g urea and 5g37% mixes, pouring in the four-hole boiling flask that condenser is housed, add the 0.2g trolamine pH value of solution is transferred to 9, is that 50 ℃, stirring velocity are under the 1500rpm condition in temperature then, reacted 2 hours, and prepared urea aldehyde performed polymer;
(2) 3g sublimed sulphur and 3.6g tolylene diisocyanate are poured in the beaker, stirred 5min, prepare oil phase; 0.5g Tween61 is joined in the aqueous gelatin solution of 20g 10%, prepare water; Oil phase is slowly joined aqueous phase, and high-speed stirring 10min forms emulsion under the rotating speed of 12000rpm, and emulsion is transferred in the four-hole boiling flask;
(3) contain the aqueous solution of 1g quadrol and 1g diethylenetriamine with constant pressure funnel Dropwise 5 4g in four-hole boiling flask, after dripping, stirred 2 hours;
(4) the urea aldehyde performed polymer for preparing is added in the four-hole boiling flask, adds 0.3g formic acid, the pH value of regulator solution is 4, is that 75 ℃, stirring velocity are to react 8 hours under the condition of 750rpm in temperature;
(5) pour out reaction solution, wait drop to room temperature after, suction filtration, washing, it is dry to put into baking oven, again trichloromethane and product is mixed stirring, the sulphur that coats on the flush away microcapsule shell wall, it is dry to continue to put into baking oven, can obtain 10.9g bilaminar membrane sulfur microcapsule product.
Bilaminar membrane sulfur microcapsule sem observation of the present invention, product diameter are in 2～7 mu m ranges, and the massfraction of sulphur is 25.2%.
Embodiment 2
The quality of each component of preparation bilaminar membrane sulfur microcapsule is as follows:
Sublimed sulphur 4.6g
Urea 3g
37% formaldehyde solution 6g
Trolamine 0.25g
Tween?61 0.6g
Gelatin 2g
Tolylene diisocyanate 4.6g
Water 70g
Formic acid 0.6g
Diethylenetriamine 2g
Quadrol 0.5g
The preparation method of bilaminar membrane sulfur microcapsule is as follows:
(1) formalin with 3g urea and 6g37% mixes, pouring in the four-hole boiling flask that condenser is housed, add the 0.25g trolamine pH value of solution is transferred to 9, is that 50 ℃, stirring velocity are under the 1300rpm condition in temperature then, reacted 2 hours, and prepared urea aldehyde performed polymer;
(2) 4.6g sublimed sulphur and 4.6g tolylene diisocyanate are poured in the beaker, stirred 5min, prepare oil phase; 0.6gTween 61 is joined in the aqueous gelatin solution of 20g 10%, prepare water; Oil phase is slowly joined aqueous phase, and high-speed stirring 10min forms emulsion under the rotating speed of 13000rpm, and emulsion is transferred in the four-hole boiling flask;
(3) contain the aqueous solution of 0.5g quadrol and 2g diethylenetriamine with constant pressure funnel Dropwise 5 4.5g in four-hole boiling flask, after dripping, stirred 2 hours;
(4) the urea aldehyde performed polymer for preparing is added in the four-hole boiling flask, adds 0.6g formic acid, the pH value of regulator solution is 4, is that 75 ℃, stirring velocity are reaction 8 hours under the condition of 1200rpm in temperature;
(5) pour out reaction solution, wait drop to room temperature after, suction filtration, washing, it is dry to put into baking oven, again trichloromethane and product is mixed stirring, the sulphur that coats on the flush away microcapsule shell wall, it is dry to continue to put into baking oven, can obtain 12.5g bilaminar membrane sulfur microcapsule product.
Bilaminar membrane sulfur microcapsule sem observation of the present invention, product diameter are in 0.5～3 mu m range, and the massfraction of sulphur is 34.4%.
Embodiment 3
The quality of each component of preparation bilaminar membrane sulfur microcapsule is as follows:
Sublimed sulphur 7.8g
Urea 3.5g
37% formaldehyde solution 7g
Trolamine 0.3g
Tween?65 0.7g
Gelatin 2g
Tolylene diisocyanate 5.5g
Water 70g
Formic acid 0.5g
Diethylenetriamine 2g
Quadrol 1.5g
The preparation method of bilaminar membrane sulfur microcapsule is as follows:
(1) formalin with 3.5g urea and 7g 37% mixes, pouring in the four-hole boiling flask that condenser is housed, add the 0.3g trolamine pH value of solution is transferred to 9, is that 50 ℃, stirring velocity are under the 1350rpm condition in temperature then, reacted 2 hours, and prepared urea aldehyde performed polymer;
(2) 7.8g sublimed sulphur and 5.5g tolylene diisocyanate are poured in the beaker, stirred 5min, prepare oil phase; 0.7gTween 65 is joined in the aqueous gelatin solution of 20g 10%, prepare water; Oil phase is slowly joined aqueous phase, and high-speed stirring 10min forms emulsion under the rotating speed of 14500rpm, and emulsion is transferred in the four-hole boiling flask;
(3) contain the aqueous solution of 1.5g quadrol and 2g diethylenetriamine with constant pressure funnel Dropwise 5 5.5g in four-hole boiling flask, after dripping, stirred 2 hours;
(4) the urea aldehyde performed polymer for preparing is added in the four-hole boiling flask, adds 0.5g formic acid, the pH value of regulator solution is 4, is that 75 ℃, stirring velocity are to react 8 hours under the condition of 750rpm in temperature;
(5) pour out reaction solution, wait drop to room temperature after, suction filtration, washing, it is dry to put into baking oven, again trichloromethane and product is mixed stirring, the sulphur that coats on the flush away microcapsule shell wall, it is dry to continue to put into baking oven, can obtain 17.8g bilaminar membrane sulfur microcapsule product.
Bilaminar membrane sulfur microcapsule sem observation of the present invention, product diameter are in 1.5～7 mu m ranges, and the massfraction of sulphur is 41.2%.
Embodiment 4
The quality of each component of preparation bilaminar membrane sulfur microcapsule is as follows:
Sublimed sulphur 9g
Urea 4g
37% formaldehyde solution 8g
Trolamine 0.35g
Tween?81 0.7g
Gelatin 2g
Tolylene diisocyanate 6g
Water 70g
Formic acid 0.5g
Diethylenetriamine 2.5g
Quadrol 1.5g
The preparation method of bilaminar membrane sulfur microcapsule is as follows:
(1) formalin with 4g urea and 8g 37% mixes, pouring in the four-hole boiling flask that condenser is housed, add the 0.35g trolamine pH value of solution is transferred to 9, is that 50 ℃, stirring velocity are under the 1350rpm condition in temperature then, reacted 2 hours, and prepared urea aldehyde performed polymer;
(2) 9g sublimed sulphur and 6g tolylene diisocyanate are poured in the beaker, stirred 5min, prepare oil phase; 0.7g Tween81 is joined in the aqueous gelatin solution of 20g 10%, prepare water; Oil phase is slowly joined aqueous phase, and high-speed stirring 10min forms emulsion under the rotating speed of 15000rpm, and emulsion is transferred in the four-hole boiling flask;
(3) contain the aqueous solution of 1.5g quadrol and 2.5g diethylenetriamine with constant pressure funnel Dropwise 5 6g in four-hole boiling flask, after dripping, stirred 2 hours;
(4) the urea aldehyde performed polymer for preparing is added in the four-hole boiling flask, adds 0.5g formic acid, the pH value of regulator solution is 4, is that 75 ℃, stirring velocity are to react 8 hours under the condition of 1100rpm in temperature;
(5) pour out reaction solution, wait drop to room temperature after, suction filtration, washing, it is dry to put into baking oven, again trichloromethane and product is mixed stirring, the sulphur that coats on the flush away microcapsule shell wall, it is dry to continue to put into baking oven, can obtain 19.5g bilaminar membrane sulfur microcapsule product.
Bilaminar membrane sulfur microcapsule sem observation of the present invention, product diameter are in 0.8～6 mu m range, and the massfraction of sulphur is 44.3%.
Embodiment 5
The quality of each component of preparation bilaminar membrane sulfur microcapsule is as follows:
Sublimed sulphur 10.5g
Urea 2g
37% formaldehyde solution 4g
Trolamine 0.35g
Tween?85 0.8g
Gelatin 2g
Tolylene diisocyanate 5g
Water 70g
Formic acid 0.8g
Diethylenetriamine 2g
Quadrol 1g
The preparation method of bilaminar membrane sulfur microcapsule is as follows:
(1) formalin with 2g urea and 4g 37% mixes, pouring in the four-hole boiling flask that condenser is housed, add the 0.35g trolamine pH value of solution is transferred to 9, is that 50 ℃, stirring velocity are under the 1250rpm condition in temperature then, reacted 2 hours, and prepared urea aldehyde performed polymer;
(2) 10.5g sublimed sulphur and 5g tolylene diisocyanate are poured in the beaker, stirred 5min, prepare oil phase; 0.8gTween 85 is joined in the aqueous gelatin solution of 20g 10%, prepare water; Oil phase is slowly joined aqueous phase, and high-speed stirring 10min forms emulsion under the rotating speed of 13000rpm, and emulsion is transferred in the four-hole boiling flask;
(3) contain the aqueous solution of 1g quadrol and 2g diethylenetriamine with constant pressure funnel Dropwise 5 5g in four-hole boiling flask, after dripping, stirred 2 hours;
(4) the urea aldehyde performed polymer for preparing is added in the four-hole boiling flask, adds 0.8g formic acid, the pH value of regulator solution is 4, is that 75 ℃, stirring velocity are to react 8 hours under the condition of 1200rpm in temperature;
(5) pour out reaction solution, wait drop to room temperature after, suction filtration, washing, it is dry to put into baking oven, again trichloromethane and product is mixed stirring, the sulphur that coats on the flush away microcapsule shell wall, it is dry to continue to put into baking oven, can obtain 19.3g bilaminar membrane sulfur microcapsule product.
Bilaminar membrane sulfur microcapsule sem observation of the present invention, product diameter are in 0.5～4 mu m range, and the massfraction of sulphur is 52.8%.
Claims (7)
1. the preparation method of a bilaminar membrane sulfur microcapsule is characterized in that, this preparation method may further comprise the steps:
(1) formalin with urea and 37% mixes, pouring in the four-hole boiling flask that condenser is housed, with trolamine the pH value of solution is transferred to 9, is that 50 ℃, stirring velocity are under 1050～1500rpm condition in temperature then, reacted 2 hours, and prepared urea aldehyde performed polymer;
(2) sulphur and tolylene diisocyanate are poured in the beaker, stirred 5 minutes, prepare oil phase; Emulsifying agent is added in the aqueous gelatin solution, prepare water; Oil phase is slowly joined aqueous phase, and high-speed stirring 10min forms emulsion, and emulsion is transferred in the four-hole boiling flask;
(3) in four-hole boiling flask, drip the aqueous solution that contains quadrol and diethylenetriamine with constant pressure funnel, after dripping, stirred 2 hours;
(4) the urea aldehyde performed polymer for preparing is added in the four-hole boiling flask, adds formic acid, the pH value of regulator solution is 4, is that 60～75 ℃, stirring velocity are to react 8 hours under the condition of 750～1200rpm in temperature;
(5) pour out reaction solution, wait drop to room temperature after, suction filtration, washing, it is dry to put into baking oven, again organic solvent and product is mixed stirring, the sulphur that coats on the flush away microcapsule shell wall, it is dry to continue to put into baking oven, can obtain the bilaminar membrane sulfur microcapsule product.
2. the preparation method of bilaminar membrane sulfur microcapsule according to claim 1 is characterized in that: second layer shell material urea-formaldehyde resin has improved the compactness of parcel sulphur and the thermostability of microcapsule.
3. the preparation method of bilaminar membrane sulfur microcapsule according to claim 1 is characterized in that: the bivalve layer that cyst material is made up of polyureas and two kinds of materials of urea-formaldehyde resin.
4. the preparation method of bilaminar membrane sulfur microcapsule according to claim 1, it is characterized in that: the emulsifying agent of preparation bilaminar membrane sulfur microcapsule is nonionic surface active agent commonly used, the HLB value is between 8～18, as Tween61 or Tween81 or Tween65 or Tween85.
5. the preparation method of bilaminar membrane sulfur microcapsule according to claim 1, it is characterized in that: described organic solvent density is at 1.4～2g/cm
3Between, and can not dissolution of sulphur.
6. the preparation method of bilaminar membrane sulfur microcapsule according to claim 1, it is characterized in that: the massfraction of sulphur is 25～53% in the described bilaminar membrane sulfur microcapsule.
7. the preparation method of bilaminar membrane sulfur microcapsule according to claim 1, it is characterized in that: described sulfur microcapsule particle diameter is between 0.5～7 μ m.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101701056B (en) * | 2009-10-21 | 2012-08-08 | 中国石油大学(北京) | Preparation method of sulphur microcapsule used as rubber vulcanizing agent |
| CN112390985A (en) * | 2020-11-14 | 2021-02-23 | 际华三五一七橡胶制品有限公司 | Preparation method of high-dispersion low-migration long-acting stable multilayer coated sulfur |
| CN113072616A (en) * | 2021-03-29 | 2021-07-06 | 浙江大学舟山海洋研究中心 | Functional peptide microcapsule for promoting proliferation of osteogenic precursor cells and preparation method thereof |
| CN114653315A (en) * | 2022-03-31 | 2022-06-24 | 山东大学 | gelatin-Arabic gum/urea resin double-layer wall material DCOIT microcapsule and preparation method and application thereof |
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| CN103222463B (en) * | 2013-03-26 | 2014-10-15 | 中国农业科学院烟草研究所 | Method for preparing 2-amino-5-thiol-1, 3, 4-thiadiazole copper controlled-release microcapsule and prepared microcapsule |
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| CN1322044C (en) * | 2005-08-16 | 2007-06-20 | 上海工程技术大学 | Microcapsulized expansion type flame-proof rubber and its preparation method |
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- 2009-01-15 CN CN2009100051093A patent/CN101475730B/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101701056B (en) * | 2009-10-21 | 2012-08-08 | 中国石油大学(北京) | Preparation method of sulphur microcapsule used as rubber vulcanizing agent |
| CN112390985A (en) * | 2020-11-14 | 2021-02-23 | 际华三五一七橡胶制品有限公司 | Preparation method of high-dispersion low-migration long-acting stable multilayer coated sulfur |
| CN112390985B (en) * | 2020-11-14 | 2022-04-29 | 际华三五一七橡胶制品有限公司 | Preparation method of high-dispersion low-migration long-acting stable multilayer coated sulfur |
| CN113072616A (en) * | 2021-03-29 | 2021-07-06 | 浙江大学舟山海洋研究中心 | Functional peptide microcapsule for promoting proliferation of osteogenic precursor cells and preparation method thereof |
| CN113072616B (en) * | 2021-03-29 | 2022-05-31 | 浙江大学舟山海洋研究中心 | Functional peptide microcapsule for promoting proliferation of osteogenic precursor cells and preparation method thereof |
| CN114653315A (en) * | 2022-03-31 | 2022-06-24 | 山东大学 | gelatin-Arabic gum/urea resin double-layer wall material DCOIT microcapsule and preparation method and application thereof |
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