CN109337039A - A kind of preparation method of micrograde polymer tiny balloon - Google Patents

A kind of preparation method of micrograde polymer tiny balloon Download PDF

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Publication number
CN109337039A
CN109337039A CN201811094752.3A CN201811094752A CN109337039A CN 109337039 A CN109337039 A CN 109337039A CN 201811094752 A CN201811094752 A CN 201811094752A CN 109337039 A CN109337039 A CN 109337039A
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Prior art keywords
tiny balloon
preparation
solid
lotion
mixture
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CN201811094752.3A
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CN109337039B (en
Inventor
杨晓武
辛燕
李培枝
秋列维
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Shaanxi Jingge Special Catalytic Technology Co ltd
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Shaanxi University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/04—Making microcapsules or microballoons by physical processes, e.g. drying, spraying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C08J2201/052—Inducing phase separation by thermal treatment, e.g. cooling a solution
    • C08J2201/0524—Inducing phase separation by thermal treatment, e.g. cooling a solution the liquid phase being aqueous
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/08—Polyurethanes from polyethers

Abstract

The present invention relates to a kind of preparation methods of micrograde polymer tiny balloon, and polyethers and polyisocyanates are uniformly mixed, and heat up and react, obtain polyurethane and isocyanate mixture；Cooling gained mixture, stirs evenly with water, obtains lotion；Using the cooling gained lotion of liquid nitrogen, ice blocks of solid is obtained；Obtained ice blocks of solid is dried in vacuo, obtains tiny balloon after dry.The present invention does not use catalyst, moisture is avoided to intervene too early by the optimization to preparation method, introduces cooling down operation, simplifies preparation step, and nuisance residual is few, and tiny balloon shape and structure obtained rule, can be applied to biomaterial and field of medical materials.

Description

A kind of preparation method of micrograde polymer tiny balloon
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of preparation side of micrograde polymer tiny balloon Method.
Background technique
There is the spherical particle of hollow features to have the function of accommodating other substances.Especially when the diameter of spherical particle is micro- When meter level or nanoscale, this microballoon just has that density is small, feature of large specific surface area, has to receiving substance therein There is covering power strong and the characteristic of high load capacity.When being not filled with other substances, it can be used as thermal and sound insulating materials.Fill medicine When object isoreactivity object, it can control release and used as microreactor.When catalyst filling, then catalysis can be greatly improved Efficiency.So the tiny balloon of micro/nano-scale has played important function in the preparation of advanced material.
The preparation of hollow microsphere usually does template using a spherical inner core, and polymer is made to assemble life around kernel It is long, it forms bead and moves back except kernel.Different polymer needs to use different kernels, and the removal mode difference of kernel is very Greatly, so to will result in different tiny balloon property different.For example it when the formation of polyacrylic microballoon, needs first with containing Carboxylic monomer aggregates into kernel, then is just further reacted in core surface with no carboxylic monomer and form shell, is finally made using alkali Kernel ionizes and water swelling is to form hollow microsphere.This process has high requirement, response procedures to monomer ratio It is more, it is easy to appear mistake.Also have and use nanometer grade silica as kernel, wrap up one layer of polymeric on surface, wrapped up After the completion of journey, dissolve kernel using hydrogen fluoride solution, this tiny balloon to be prepared into power higher, but remove silica Shi Biran leads to a large amount of fluorine residue, affects such hollow microsphere in the application of biological field.It was formed in different microballoons , there is shell forming process complexity in Cheng Zhong, kernel removes difficult problem.
Chinese patent CN108192074, which is disclosed, a kind of prepares cross-linked polyurethane micro-balls and/or poly- using self-emulsifying technology The method of urethane tiny balloon, do not use organic solvent, but in order to or complicated network-like polymer architecture need to use official The polymer and organo-metallic catalyst that energy degree is 3 or more.These organic metal are protected in drying process in the invention It stays in the product, so that the product can not be applied to biomaterial and medical material.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of micrograde polymer tiny balloon, participate in the raw material kind of reaction Class is few, and hollow microsphere forming process is simple.
The technical scheme adopted by the invention is that:
A kind of preparation method of micrograde polymer tiny balloon, preparation step are as follows:
10 parts of polyethers and 15 ~ 20 parts of polyisocyanates are uniformly mixed, are warming up to 50 ~ 70 DEG C, react 20 ~ 30min by step 1, Obtain polyurethane and isocyanate mixture；
Step 2, one gained mixture of cooling step, stirs evenly with the water of 9 ~ 10 times of quality of mixture, obtains lotion；
Step 3 obtains ice blocks of solid using two gained lotion of liquid nitrogen cooling step；
Step 4, the ice blocks of solid that step 3 is obtained are dried in vacuo, and drying pressure is 5 ~ 10Pa, are obtained after dry hollow micro- Ball.
In step 1, polyethers is the polyglycol ether that average molecular mass is 350 ~ 450g/mol, and one end is hydroxyl, The other end is torpescence alkyl.
In step 1, polyisocyanates is the isocyanates containing more than two isocyanate group, is that isophorone two is different Cyanate (IPDI), hexamethylene diisocyanate (HDI) or HDI trimer.
The invention has the following advantages that
1. preparation method raw material of the invention is simple, polyethers and isocyanates are only included, does not use catalyst.
2. preparation step is few, easy to operate, one is divided into mixing temperature reaction, emulsification, cooling, dry four steps, i.e., Tiny balloon can be prepared；Heating up process is the process to form the case material with emulsifying capacity, mixed with water later It closes, can control that hydrolysis ratio prevents isocyanates hydrolyzes to form amino acid, avoids because of lotion caused by emulsifying in advance Or suspension is extremely unstable.
3. introducing cooling down operation, unreacted isocyanates, after being frozen into solid, distil gasification under lower pressure, with Gas form leaves cavity by shell.Be frozen into ice cube water may insure tiny balloon formed before, spheric granules with Keep what certain distance prevented spheric granules to be adhered deformation between grain.
4. preparation process nuisance residual is few, harmful small molecule involved in process is isocyanates, and isocyanates is pair The active substance of hydroxyl, though not over vacuum drying the step for thoroughly remove, also can in storing process with active hydrogen or Water in person and air reacts and loses toxicity.
5. the rule of tiny balloon shape and structure made from due to having used core liquid in preparation process, and is removed thoroughly, Regular surfaces are all presented in gained tiny balloon inner wall and appearance, facilitate microballoon hollow cavity volume estimation.
Detailed description of the invention
Fig. 1 is one micrograde polymer tiny balloon microscopic appearance of embodiment.
Specific embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail, but embodiments of the present invention include But it is not limited to the range of following embodiment expression.
Preparation of the invention the preparation method is as follows:
10 parts of polyethers and 15 ~ 20 parts of polyisocyanates are uniformly mixed, are warming up to 50 ~ 70 DEG C, react 20 ~ 30min by step 1, Obtain polyurethane and isocyanate mixture；
Step 2, one gained mixture of cooling step, stirs evenly with the water of 9 ~ 10 times of quality of mixture, obtains lotion；
Step 3 obtains ice blocks of solid using two gained lotion of liquid nitrogen cooling step；
Step 4, the ice blocks of solid that step 3 is obtained are dried in vacuo, and drying pressure is 5 ~ 10Pa, are obtained after dry hollow micro- Ball.
In step 1, polyethers is the polyglycol ether that average molecular mass is 350 ~ 450g/mol, and one end is hydroxyl, The other end is torpescence alkyl.
In step 1, polyisocyanates is the isocyanates containing more than two isocyanate group, is that isophorone two is different Cyanate (IPDI), hexamethylene diisocyanate (HDI) or HDI trimer.
Preparation principle of the invention is, is oily phase with isocyanates, with isocyanates and polyether reactant using water as continuous phase Gained polyurethane is that surfactant forms lotion.Isocyanates is oil phase liquid, the base that the isocyanates in polyurethane is brought into Group is similar to polyurethane structural, so can emulsify isocyanates.Since emulsifier is not small molecule, isocyanates liquid after emulsification It is thick and solid shell structurre around drop, this may insure have enough intensity that can stablize storage after tiny balloon is formed.Thick and solid Shell structurre also can prevent moisture and isocyanates contact free simultaneously, delay isocyanates because water there are due to quickly become Matter.A small amount of moisture, which contacts the polyurethane structural to be formed with isocyanates, can be used as supplement to shell structurre intensity.It is not anti- The isocyanates answered, after being frozen into solid, distil gasification under lower pressure.With gas form by shell, cavity is left.Freeze Form ice cube water may insure that tiny balloon is formed before, keep certain distance to prevent spherical between spheric granules and particle Grain is adhered deformation.
The present invention is explained in detail below by specific embodiment.
Embodiment 1
15 parts of hexamethylene diisocyanate HDI and 10 parts of polyglycol ethers are weighed, wherein average opposite point of polyglycol ether Protonatomic mass is 350g/mol, and polyethers one end is hydroxyl, and one end is methyl, and the two is uniformly mixed and is reacted under the conditions of 60 DEG C 30min.Gained mixture is cooled to room temperature, water 225g is added, stirring forms lotion.Lotion is quickly cooled to admittedly with liquid nitrogen Body.Obtained solid is placed in vacuum desiccator, sets pressure as 5Pa, after drying for 24 hours, obtained solid is polymer Tiny balloon.1 ~ 5 μm of microsphere diameter, thickness of shell is 300 ~ 500nm, as shown in Figure 1.
Embodiment 2
20g isophorone diisocyanate IPDI and 10g polyglycol ether are weighed, wherein the averagemolecular wt of polyglycol ether Quality is 450g/mol, and polyethers one end is hydroxyl, and one end is ethyl, and the two is uniformly mixed and reacts 30min under the conditions of 60 DEG C. Gained mixture is cooled to room temperature, water 300g is added, stirring forms lotion.Lotion is quickly cooled to solid with liquid nitrogen.By institute It obtains solid to be placed in vacuum desiccator, sets pressure as 5Pa, after 30h is dry, obtained solid is that polymeric hollow is micro- Ball.1 ~ 10 μm of microsphere diameter, thickness of shell is 200 ~ 600nm.
Embodiment 3
15gHDI tripolymer and 10g polyglycol ether are weighed, wherein the average molecular mass of polyglycol ether is 350g/ Mol, polyethers one end are hydroxyl, and one end is methyl, and the two is uniformly mixed and reacts 20min under the conditions of 60 DEG C.Gained is mixed Object is cooled to room temperature, and adds water 250g, and stirring forms lotion.Lotion is quickly cooled to solid with liquid nitrogen.Obtained solid is placed in In vacuum desiccator, pressure is set as 10Pa, after drying for 24 hours, obtained solid is polymer hollow microsphere.Microsphere diameter 1 ~ 5 μm, thickness of shell is 300 ~ 500nm.
Above embodiments 1 are most preferred embodiment.
The contents of the present invention are not limited to cited by embodiment, and those of ordinary skill in the art are by reading description of the invention And to any equivalent transformation that technical solution of the present invention is taken, all are covered by the claims of the invention.

Claims (3)

1. a kind of preparation method of micrograde polymer tiny balloon, it is characterised in that:
The following steps are included:
10 parts of polyethers and 15 ~ 20 parts of polyisocyanates are uniformly mixed, are warming up to 50 ~ 70 DEG C, react 20 ~ 30min by step 1, Obtain polyurethane and isocyanate mixture；
Step 2, one gained mixture of cooling step, stirs evenly with the water of 9 ~ 10 times of quality of mixture, obtains lotion；
Step 3 obtains ice blocks of solid using two gained lotion of liquid nitrogen cooling step；
Step 4, the ice blocks of solid that step 3 is obtained are dried in vacuo, and drying pressure is 5 ~ 10Pa, are obtained after dry hollow micro- Ball.
2. a kind of preparation method of micrograde polymer tiny balloon according to claim 1, it is characterised in that:
In step 1, polyethers is the polyglycol ether that average molecular mass is 350 ~ 450g/mol, and one end is hydroxyl, another End is torpescence alkyl.
3. a kind of preparation method of micrograde polymer tiny balloon according to claim 1 or 2, it is characterised in that:
In step 1, polyisocyanates is the isocyanates containing more than two isocyanate group, is isophorone diisocyanate Ester (IPDI), hexamethylene diisocyanate (HDI) or HDI trimer.
CN201811094752.3A 2018-09-19 2018-09-19 Preparation method of micron-sized polymer hollow microspheres Active CN109337039B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109867532A (en) * 2019-04-15 2019-06-11 梁剑 A kind of insulating board for building and preparation method thereof
CN112679941A (en) * 2020-12-24 2021-04-20 山东龙祥新材料科技有限公司 High-strength sound-insulation polyurethane-urea composite material

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005113631A1 (en) * 2004-05-18 2005-12-01 Basf Aktiengesellschaft Syntactic polyurethanes and the use thereof of for off-shore shore damping
EP1908576A1 (en) * 2006-10-02 2008-04-09 ERA BESCHICHTUNG GmbH & CO. KG Application of a polyvinyl foam material in vehicle construction
CN101249077A (en) * 2008-04-14 2008-08-27 西南交通大学 Preparation of degradable pollutant polyalcohol stephanoporate microballoons and uses thereof
CN107216629A (en) * 2017-05-05 2017-09-29 武汉理工大学 A kind of hollow glass micropearl and polyurethane modified synergic unsaturated polyester composite and preparation method thereof
CN108192074A (en) * 2016-12-08 2018-06-22 万华化学集团股份有限公司 A kind of preparation method of cross-linked polyurethane micro-balls and/or polyurethane tiny balloon

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005113631A1 (en) * 2004-05-18 2005-12-01 Basf Aktiengesellschaft Syntactic polyurethanes and the use thereof of for off-shore shore damping
EP1908576A1 (en) * 2006-10-02 2008-04-09 ERA BESCHICHTUNG GmbH & CO. KG Application of a polyvinyl foam material in vehicle construction
CN101249077A (en) * 2008-04-14 2008-08-27 西南交通大学 Preparation of degradable pollutant polyalcohol stephanoporate microballoons and uses thereof
CN108192074A (en) * 2016-12-08 2018-06-22 万华化学集团股份有限公司 A kind of preparation method of cross-linked polyurethane micro-balls and/or polyurethane tiny balloon
CN107216629A (en) * 2017-05-05 2017-09-29 武汉理工大学 A kind of hollow glass micropearl and polyurethane modified synergic unsaturated polyester composite and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109867532A (en) * 2019-04-15 2019-06-11 梁剑 A kind of insulating board for building and preparation method thereof
CN112679941A (en) * 2020-12-24 2021-04-20 山东龙祥新材料科技有限公司 High-strength sound-insulation polyurethane-urea composite material
CN112679941B (en) * 2020-12-24 2023-03-03 山东龙祥新材料科技有限公司 High-strength sound-insulation polyurethane-urea composite material

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