CN110041465A - A kind of mono dispersed micrograde elastic microsphere powder and its preparation method and application - Google Patents

A kind of mono dispersed micrograde elastic microsphere powder and its preparation method and application Download PDF

Info

Publication number
CN110041465A
CN110041465A CN201910267192.5A CN201910267192A CN110041465A CN 110041465 A CN110041465 A CN 110041465A CN 201910267192 A CN201910267192 A CN 201910267192A CN 110041465 A CN110041465 A CN 110041465A
Authority
CN
China
Prior art keywords
methyl
acrylate
suspension
elastic microsphere
microsphere powder
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
CN201910267192.5A
Other languages
Chinese (zh)
Inventor
何宇
林俊杰
曾义
刘泽鹏
杨德彬
贾国忠
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
GUANGZHOU WUXING MATERIAL TECHNOLOGY Co Ltd
Original Assignee
GUANGZHOU WUXING MATERIAL TECHNOLOGY Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by GUANGZHOU WUXING MATERIAL TECHNOLOGY Co Ltd filed Critical GUANGZHOU WUXING MATERIAL TECHNOLOGY Co Ltd
Priority to CN201910267192.5A priority Critical patent/CN110041465A/en
Publication of CN110041465A publication Critical patent/CN110041465A/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/18—Suspension polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4808—Mixtures of two or more polyetherdiols
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • 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
    • 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
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • 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
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group
    • C08G18/7642—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group containing at least two isocyanate or isothiocyanate groups linked to the aromatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate groups, e.g. xylylene diisocyanate or homologues substituted on the aromatic ring
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C08J3/122—Pulverisation by spraying
    • 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
    • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2351/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention belongs to technical field of macromolecule polymerization, a kind of mono dispersed micrograde elastic microsphere powder and its preparation method and application is disclosed.The microballoon powder is that urethane acrylate and vinyl monomer are mixed to get prepolymer, it is added after initiator and stabilizer and pre- suspension is prepared by free radical polymerization, pre- suspension is passed through nitrogen, polymer suspension is obtained after heating, polymer suspension is dried obtained；The urethane acrylate is that polyalcohol is added dropwise in isocyanates, then is blocked to obtain by hydroxy acryl acid ester monomer.The method of the present invention is simple, and without using any solvent, is advantageously implemented the industrialized production and application of microballoon.Resulting polymers microballoon has high resiliency and monodispersity, can effectively control elasticity, partial size and the particle diameter distribution of product by simply changing experiment condition, can be widely used in cosmetics and coating, increases elasticity and sense of touch.

Description

A kind of mono dispersed micrograde elastic microsphere powder and its preparation method and application
Technical field
The invention belongs to technical field of macromolecule polymerization, more particularly, to a kind of mono dispersed micrograde elastic microsphere powder Body and its preparation method and application.
Background technique
Polymer elasticity microballoon is due to being widely used in each of daily life with excellent elasticity and lubricity In field.For example, cosmetics, resin and modified paint, biological medicine.Polymer elasticity microballoon mainly passes through precipitation polymerization at present It is prepared with emulsion polymerization.Wherein precipitation polymerization is the effective ways for preparing the controllable polymer microballoon of form, in recent years by Concern.Compared with emulsion polymerization, dispersin polymerization has many advantages, such as products pure, particle size narrowly distributing；But pass through precipitation polymerization system When standby microballoon, the crosslink density in system is extremely low, because crosslinking agent is added in precipitation polymerization system will lead to microballoon deformation, even Form gel；Precipitation Polymerization Process prepares micrograde polymer microsphere because solvent processing, polymer microballoon low yield etc. are asked simultaneously It inscribes and is gradually substituted by other polymerization techniques.Patent CN 106854267A is exactly the method using precipitation polymerization, is made with acetonitrile It is prepared for that there is elastomeric polyaminoester microball for solvent, although its preparation process is simple, because its microballoon is uncrosslinked, answers It will greatly be limited with range.
Patent CN 103421191A report uses emulsion polymerization, prepares organosilicon using starch granules as emulsifier Lotion, and organosilicone elastic microballoon is made by Si―H addition reaction.However, time-consuming by the preparation process of the polymerization, changes method preparation and change Property starch granules need 1-10 days, emulsion polymerization need for 24 hours.And obtained organosilicone elastic microsphere surface adheres to a large amount of starch Grain, so can not be removed in the later period by techniques such as washings, is applied since such starch granules has passed through hydrophobically modified in the later period When remaining starch granules luminous flux can be greatly reduced, cause product light penetration low, phenomena such as whitening.As solve this The method of a little problems, it is well known that suspension polymerisation is equally the method for preparing polymer elasticity microballoon, and uses suspension polymerization Prepare polymer elasticity microballoon have the advantages that heat dissipation be easy, can Batch Process, more most important is products pure, solvent-free Etc byproduct emission, widened the application range of product to a certain extent.
Summary of the invention
In order to solve above-mentioned the shortcomings of the prior art, primary and foremost purpose of the present invention is to provide a kind of monodisperse Micron order elastic microsphere powder.The microballoon powder has excellent elasticity and relatively narrow particle size span.
Another object of the present invention is to provide above-mentioned mono dispersed micrograde elastic microsphere raw powder's production technologies.The present invention A kind of urethane acrylate is prepared first, then again mixes the urethane acrylate monomer being prepared with vinyl monomer It closes, the suspension containing polymer elasticity microballoon is obtained by free radical polymerization, it is finally that dewatering suspensions are dry, obtain single point Dissipate micron order elastic microsphere powder.
A further object of the present invention is to provide the applications of above-mentioned mono dispersed micrograde elastic microsphere powder.
The purpose of the present invention is realized by following technical proposals:
A kind of mono dispersed micrograde elastic microsphere powder, the microballoon powder are by urethane acrylate and vinyl list Body is mixed to get prepolymer, is added after initiator and stabilizer and prepares pre- suspension by free radical polymerization, pre- suspension is led to Enter nitrogen, obtain polymer suspension after heating, polymer suspension is dried obtained；The urethane acrylate is Polyalcohol is added dropwise in isocyanates, then is blocked to obtain by hydroxy acryl acid ester monomer.
Preferably, the polyalcohol is dihydric alcohol, and the dihydric alcohol is polypropylene glycol, polytetrahydrofuran diol, gathers oneself two One or more of sour glycol ester, poly adipate succinic acid ester, polycaprolactone glycol, polycarbonate glycol.
Preferably, the isocyanates is benzene dimethylene diisocyanate, isophorone diisocyanate, hexa-methylene One or more of diisocyanate or 4,4'- dicyclohexyl methyl hydride diisocyanate；The hydroxy acryl acid ester monomer is (methyl) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate, (methyl) hy-droxybutyl or caprolactone modification (methyl) third One or more of olefin(e) acid ester.
Preferably, the vinyl monomer is (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid N-propyl, (methyl) n-butyl acrylate, (methyl) cyclohexyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid Last of the ten Heavenly stems ester, (methyl) lauryl acrylate, 17 ester of (methyl) acrylic acid, (methyl) octadecyl acrylate, (methyl) acrylic acid two One or more of ten diester or isobornyl (methyl) acrylate.
Preferably, the stabilizer is lauryl sodium sulfate, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, cetyl two Phenylate sodium disulfonate, sodium dioctylsuccinate, lauryl alcohol polyethers sodium sulphate, dodecyl sodium sulfate or dodecyl benzene sulfonic acid Sodium, TRITONTMX-305、TERGITOLTM15-S-20、TERGITOLTMTMN-100X、ECOSURFTMEH-9、 TERGITOLTM26-L-9 or ECOSURFTMOne or more of SA-15.
Preferably, the initiator is organic peroxide and azo initiators.
It is further preferable that the organic peroxide is benzoyl peroxide, lauroyl peroxide, peroxidating neopentanoic acid One or more of tert-pentyl ester, peroxidating 2 ethyl hexanoic acid tert-pentyl ester or peroxidating 2 ethyl hexanoic acid tert-butyl ester；The azo Series initiators are one or more of azodiisobutyronitrile, azobisisoheptonitrile or azobisisovaleronitrile.
Preferably, the mass ratio of the urethane acrylate and vinyl monomer is (3~6): (4~7)；Described is steady The mass ratio for determining agent and prepolymer is (0.1~1): 20；The mass ratio of the initiator and prepolymer is (0.5~3): 100； The number-average molecular weight of the urethane acrylate is 5000~20000；The contents of ethylene of the urethane acrylate For 0.1~1mmol/g.
The mono dispersed micrograde elastic microsphere raw powder's production technology, comprises the following specific steps that:
S1. polyalcohol is added dropwise in isocyanates, is then blocked to obtain poly- ammonia by hydroxy acryl acid ester monomer Ester acrylate；
S2. urethane acrylate and vinyl monomer mixing, stir to being completely dissolved, obtain mixed solution；
S3. the mixed solution of step S2 and initiator are added in stabiliser solution simultaneously, are dispersed and obtain pre- suspension；
S4. pre- suspension is passed through nitrogen, 4~8h is kept the temperature after being warming up to 50~80 DEG C, reaction terminates, and it is outstanding to obtain polymer Supernatant liquid；
S5. polymer suspension is dried at 105~115 DEG C, obtains mono dispersed micrograde elastic microsphere powder.
Application of the mono dispersed micrograde elastic microsphere powder in cosmetics or coating.
In addition, the present invention considers from the microballoon powder viewpoint for obtaining having favorable elasticity, preferred urethane acrylate Number-average molecular weight is 5000~20000；Further, the number-average molecular weight of prepolymer is 6000~15000.It is further preferable that The number-average molecular weight of prepolymer is 8000~12000.
Preferably, the contents of ethylene in prepolymer is 0.1~1mmol/g, further, in urethane acrylate Contents of ethylene is 0.25~0.8mmol/g；It is further preferable that the contents of ethylene in prepolymer is 0.4~0.6mmol/g.
The method that the present invention can carry out the homogeneous mixer of micronized using high-speed rotating shearing force, or produced using high pressure The ejection power of life carries out the homogenizer of micronized, the preparation side by method that high-speed stirred mixes as pre- suspension Method.Wherein, the method for using homogenizer makes the distribution narrow of the partial size of polymer suspension.In addition, from polymer point is increased The stability of dispersion liquid and the homogeneity of particle size comprehensively consider preferred dodecyl diphenyl oxide sodium sulfonate；In order to by polymer Microballoon recycles from lotion and obtains powder, and spray drying process or coacervation may be selected.
Polyalcohol is slowly added dropwise in the present invention in the presence of isocyanates first, then by hydroxy acryl acid ester monomer into Row sealing end obtains urethane acrylate.The urethane acrylate of preparation and vinyl monomer are mixed to get prepolymer, added Enter and suspension is prepared by free radical polymerization after initiator and stabilizer, is finally made suspension is dry.The polyalcohol used It is preferred that dihydric alcohol is guaranteeing product stability this is because dihydric alcohol is that the prepolymer that raw material obtains has excellent flexibility Under the premise of can obtain more flexible urethane acrylate, flexible increase of urethane acrylate is conducive to elasticity The preparation of microballoon, and in system dihydric alcohol use, be conducive to production stabilization, be less prone to gelatinization in process of production.
Compared with prior art, the invention has the following advantages:
1. resulting polymers microballoon powder of the present invention has high resiliency, monodispersity and relatively narrow particle size span.
2. stability of suspension of the invention is good, gelatinization is not easy in production process.
3. pure, solvent-free etc the byproduct emission of elastic microsphere powder of the invention, is conducive to the industrialization of microballoon Production and application.
4. the method for the present invention is simple, and without using any solvent, is advantageously implemented the industrialized production of microballoon and answers With.Elasticity, partial size and the particle diameter distribution of product can be effectively controlled by simply changing experiment condition, can widely be answered For increasing elasticity and sense of touch in cosmetics and coating.
Detailed description of the invention
Fig. 1 is the grain size distribution of mono dispersed micrograde elastic microsphere powder made from embodiment 4.
Fig. 2 is the grain size distribution of mono dispersed micrograde elastic microsphere powder made from embodiment 5.
Specific embodiment
The contents of the present invention are further illustrated combined with specific embodiments below, but should not be construed as limiting the invention. Unless otherwise specified, the conventional means that technological means used in embodiment is well known to those skilled in the art.Except non-specifically Illustrate, reagent that the present invention uses, method and apparatus is the art conventional reagents, method and apparatus.
Embodiment 1
1. 19.7g isophorone diisocyanate, 0.1g p-hydroxyanisole and 0.2g bismuth neodecanoate to be added to and be equipped with In the reaction flask of electric mixer, peristaltic pump and thermometer.Starting stirring, is warming up to 50 DEG C.It is slowly added dropwise and in advance mixes 66.6g polypropylene glycol (molecular weight 2000) and 12.5g polytetrahydrofuran diol (molecular weight 2000), by reaction temperature liter after dripping off To 80 DEG C, 4 hours are kept the temperature.It is eventually adding the 0.7g hydroxy-ethyl acrylate mixed in advance and 0.5g hydroxyethyl methacrylate carries out Sealing end, obtains urethane acrylate.
2. taking the urethane acrylate of the above-mentioned synthesis of 40g, 30g butyl acrylate is added and 30g lauryl acrylate is mixed It closes, stirs to being completely dissolved, obtain mixed solution；
3. taking 1g sodium dioctylsuccinate, 1gECOSURFTMEH-9 and 100g water are mixed with to obtain stabiliser solution.
4. by the mixed solution of step 2 and 0.5g benzoyl peroxide, 0.5g azodiisobutyronitrile, step 3 is added simultaneously Stabiliser solution in, be dispersed obtain pre- suspension；
5. pre- suspension is passed through nitrogen, 5h is kept the temperature after being warming up to 80 DEG C, reaction terminates, and obtains polymer suspension；
6. polymer suspension is spray-dried, temperature is set as 105 DEG C~115 DEG C, finally obtains monodisperse micron Grade elastic microsphere powder.
Embodiment 2
1. 39.2g4,4'- dicyclohexyl methyl hydride diisocyanate, 0.1g p-hydroxyanisole and 0.2g bismuth neodecanoate are added Enter into the reaction flask equipped with electric mixer, peristaltic pump and thermometer.Starting stirring, is warming up to 50 DEG C.It is slowly added dropwise in advance Mixed 9.6g polytetrahydrofuran diol (molecular weight 650) and 48g polycarbonate glycol (molecular weight 1000), will reaction after dripping off Temperature rises to 80 DEG C, keeps the temperature 4 hours.3.2g hydroxypropyl acrylate is eventually adding to be blocked to obtain urethane acrylate.
2. taking the urethane acrylate of the above-mentioned synthesis of 40g, 10g methyl methacrylate and 50g methacrylic acid is added The mixing of last of the ten Heavenly stems ester, stirs to being completely dissolved, obtains mixed solution；
3. taking 2g lauryl sodium sulfate, 0.5gTERGITOLTM15-S-20 and 100g water is mixed with to obtain stabilizer molten Liquid.
4. the mixed solution of step 2 and 0.5g peroxidating 2 ethyl hexanoic acid tert-pentyl ester to be added to the stabilizer of step 3 simultaneously In solution, it is dispersed and obtains pre- suspension；
5. pre- suspension is passed through nitrogen, 6h is kept the temperature after being warming up to 80 DEG C, reaction terminates, and obtains polymer suspension；
6. polymer suspension is spray-dried, temperature is set as 105 DEG C~115 DEG C, finally obtains monodisperse micron Grade elastic microsphere powder.
Embodiment 3
1. 27.7g hexamethylene diisocyanate, 0.1g p-hydroxyanisole and 0.2g bismuth neodecanoate to be added to and be equipped with In the reaction flask of electric mixer, peristaltic pump and thermometer.Starting stirring, is warming up to 50 DEG C.It is slowly added dropwise and in advance mixes 45.3g polyethylene glycol adipate (molecular weight 1000) and 22.8g polycarbonate glycol (molecular weight 1000), will reaction after dripping off Temperature rises to 80 DEG C, keeps the temperature 4 hours.It is eventually adding 0.8g hydroxyethyl methacrylate and 3.5g hy-droxybutyl is blocked Obtain urethane acrylate.
2. taking the urethane acrylate of the above-mentioned synthesis of 40g, the mixing of 60g n-propyl is added, stirs to completely molten Solution, obtains mixed solution；
3. 0.5g lauryl sodium sulfate and 100g water is taken to be mixed with to obtain stabiliser solution.
4. the steady of step 3 is added in the mixed solution of step 2 and 0.5g benzoyl peroxide, 1g lauroyl peroxide simultaneously Determine in agent solution, is dispersed and obtains pre- suspension；
5. pre- suspension is passed through nitrogen, 6h is kept the temperature after being warming up to 70 DEG C, reaction terminates, and obtains polymer suspension；
6. polymer suspension is spray-dried, temperature is set as 105 DEG C~115 DEG C, finally obtains monodisperse micron Grade elastic microsphere powder.
Embodiment 4
1. 34.7g isophorone diisocyanate, 0.1g p-hydroxyanisole and 0.2g bismuth neodecanoate to be added to and be equipped with In the reaction flask of electric mixer, peristaltic pump and thermometer.Starting stirring, is warming up to 50 DEG C.61.3g polyadipate is slowly added dropwise Reaction temperature is risen to 80 DEG C after dripping off by glycol ester (molecular weight 1000), keeps the temperature 4 hours.It is eventually adding 4.1g acrylic acid hydroxyl Ethyl ester is blocked to obtain urethane acrylate.
2. taking the urethane acrylate of the above-mentioned synthesis of 40g, 25g cyclohexyl methacrylate, 35g acrylic acid 17 is added Ester mixing, stirs to being completely dissolved, obtains mixed solution；
3. taking 1g sodium dioctylsuccinate, 1g TERGITOLTM15-S-20 and 100g water is mixed with to obtain stabilizer molten Liquid.
4. simultaneously by the mixed solution of step 2 and 1.5g peroxidating 2 ethyl hexanoic acid tert-pentyl ester, 0.5g azobisisoheptonitrile It is added in the stabiliser solution of step 3, is dispersed and obtains pre- suspension；
5. pre- suspension is passed through nitrogen, 8h is kept the temperature after being warming up to 50 DEG C, reaction terminates, and obtains polymer suspension；
6. polymer suspension is spray-dried, temperature is set as 105 DEG C~115 DEG C, finally obtains monodisperse micron Grade elastic microsphere powder.
Fig. 1 is the grain size distribution of mono dispersed micrograde elastic microsphere powder made from embodiment 4.From fig. 1, it can be seen that microballoon The particle diameter distribution of powder is relatively narrow, has relatively narrow particle size span.
Embodiment 5
1. 21.1g benzene dimethylene diisocyanate, 0.1g p-hydroxyanisole and 0.2g bismuth neodecanoate are added to dress In the reaction flask for having electric mixer, peristaltic pump and thermometer.Starting stirring, is warming up to 50 DEG C.39.7g poly- the third two is slowly added dropwise Reaction temperature is risen to 80 DEG C after dripping off by alcohol (molecular weight 2000), 34g polytetrahydrofuran diol (molecular weight 2000), and heat preservation 4 is small When.It is eventually adding 1g hydroxyethyl methacrylate, 4.2g hydroxypropyl acrylate is blocked to obtain urethane acrylate.
2. taking the urethane acrylate of the above-mentioned synthesis of 40g, it is mixed that 40g Isooctyl acrylate monomer, 20g lauryl acrylate is added It closes, stirs to being completely dissolved, obtain mixed solution；
3. 2g disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate and 100g water is taken to be mixed with to obtain stabiliser solution.
4. simultaneously by the mixed solution of step 2 and 1.5g benzoyl peroxide, 1.5g peroxidating 2 ethyl hexanoic acid tert-pentyl ester It is added in the stabiliser solution of step 3, is dispersed and obtains pre- suspension；
5. pre- suspension is passed through nitrogen, 8h is kept the temperature after being warming up to 60 DEG C, reaction terminates, and obtains polymer suspension；
6. polymer suspension is spray-dried, temperature is set as 105 DEG C~115 DEG C, finally obtains monodisperse micron Grade elastic microsphere powder.
Fig. 2 is the grain size distribution of mono dispersed micrograde elastic microsphere powder made from embodiment 5.As can be seen from Figure 2, microballoon Partial size is larger, and particle diameter distribution is relatively narrow.
Embodiment 6
1. 39.5g4,4'- dicyclohexyl methyl hydride diisocyanate, 0.1g p-hydroxyanisole and 0.2g bismuth neodecanoate are added Enter into the reaction flask equipped with electric mixer, peristaltic pump and thermometer.Starting stirring, is warming up to 50 DEG C.19.9g is slowly added dropwise Polytetrahydrofuran diol (molecular weight 650), 32g polytetrahydrofuran diol (molecular weight 2000), rise to reaction temperature after dripping off 80 DEG C, keep the temperature 4 hours.8.7g hy-droxybutyl is eventually adding to be blocked to obtain urethane acrylate.
2. taking the urethane acrylate of the above-mentioned synthesis of 40g, the mixing of 60g Isooctyl acrylate monomer is added, stirs to completely molten Solution, obtains mixed solution；
3. 2g lauryl sodium sulfate, 2g disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate and 100g water is taken to be mixed with and stablized Agent solution.
4. the mixed solution of step 2 and 2g lauroyl peroxide, 1g azobisisoheptonitrile to be added to the stabilization of step 3 simultaneously In agent solution, it is dispersed and obtains pre- suspension；
5. pre- suspension is passed through nitrogen, 5h is kept the temperature after being warming up to 70 DEG C, reaction terminates, and obtains polymer suspension；
6. polymer suspension is spray-dried, temperature is set as 105 DEG C~115 DEG C, finally obtains monodisperse micron Grade elastic microsphere powder.
Embodiment 7
1. 37.5g hexamethylene diisocyanate, 0.1g p-hydroxyanisole and 0.2g bismuth neodecanoate to be added to and be equipped with In the reaction flask of electric mixer, peristaltic pump and thermometer.Starting stirring, is warming up to 50 DEG C.25.8g polycaprolactone is slowly added dropwise Reaction temperature is risen to 80 DEG C after dripping off, heat preservation 4 by glycol (molecular weight 550), 25.7g polycarbonate glycol (molecular weight 1000) Hour.It is eventually adding 5.2g hydroxypropyl acrylate, 5.8g hy-droxybutyl is blocked to obtain urethane acrylate.
2. taking the urethane acrylate of the above-mentioned synthesis of 40g, 16g methyl methacrylate, 44g Isooctyl acrylate monomer is added Mixing stirs to being completely dissolved, obtains mixed solution；
3. 3g disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, 2g neopelex and 100g water is taken to be mixed with to obtain surely Determine agent solution.
4. step 3 is added in the mixed solution of step 2 and 0.5g benzoyl peroxide, 1.5g azodiisobutyronitrile simultaneously In stabiliser solution, it is dispersed and obtains pre- suspension；
5. pre- suspension is passed through nitrogen, 6h is kept the temperature after being warming up to 75 DEG C, reaction terminates, and obtains polymer suspension；
6. polymer suspension is spray-dried, temperature is set as 105 DEG C~115 DEG C, finally obtains monodisperse micron Grade elastic microsphere powder.
Embodiment 8
1. 44.3g benzene dimethylene diisocyanate, 0.1g p-hydroxyanisole and 0.2g bismuth neodecanoate are added to dress In the reaction flask for having electric mixer, peristaltic pump and thermometer.Starting stirring, is warming up to 50 DEG C.The poly- tetrahydro of 29.2g is slowly added dropwise Reaction temperature is risen to 80 DEG C after dripping off by furans glycol (molecular weight 650), 13.4g polycaprolactone glycol (molecular weight 550), is protected Temperature 4 hours.13.1g hydroxyethyl methacrylate is eventually adding to be blocked to obtain urethane acrylate.
2. taking the urethane acrylate of the above-mentioned synthesis of 40g, 30g n-propyl, 30g methacrylic acid hexamethylene is added Ester mixing, stirs to being completely dissolved, obtains mixed solution；
3. taking 0.5g sodium dioctylsuccinate, 0.5g ECOSURFTMEH-9 and 100g water is mixed with to obtain stabilizer molten Liquid.
4. the mixed solution of step 2 and 1.5g peroxidating 2 ethyl hexanoic acid tert-pentyl ester, 1g azobisisoheptonitrile are added simultaneously Enter in the stabiliser solution of step 3, is dispersed and obtains pre- suspension；
5. pre- suspension is passed through nitrogen, 4h is kept the temperature after being warming up to 65 DEG C, reaction terminates, and obtains polymer suspension；
6. polymer suspension is spray-dried, temperature is set as 105 DEG C~115 DEG C, finally obtains monodisperse micron Grade elastic microsphere powder.
Comparative example 1
1. 22.2g4,4'- dicyclohexyl methyl hydride diisocyanate, 0.1g p-hydroxyanisole and 0.2g bismuth neodecanoate are added Enter into the reaction flask equipped with electric mixer, peristaltic pump and thermometer.Starting stirring, is warming up to 50 DEG C.76.9g is slowly added dropwise Reaction temperature is risen to 80 DEG C after dripping off by polytetrahydrofuran diol (molecular weight 2000), keeps the temperature 4 hours.It is eventually adding 0.9g third Olefin(e) acid hydroxyl ethyl ester is blocked to obtain urethane acrylate.
2. taking the urethane acrylate of the above-mentioned synthesis of 40g, it is mixed that 40g butyl acrylate, 20g decyl-octyl methacrylate is added It closes, stirs to being completely dissolved, obtain mixed solution；
3. 1.5g lauryl sodium sulfate, 1g disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate and 100g water is taken to be mixed with to obtain surely Determine agent solution.
4. step 3 is added in the mixed solution of step 2 and 0.5g benzoyl peroxide, 0.5g azodiisobutyronitrile simultaneously In stabiliser solution, it is dispersed and obtains pre- suspension；
5. pre- suspension is passed through nitrogen, 8h is kept the temperature after being warming up to 65 DEG C, reaction terminates, and obtains polymer suspension；
6. polymer suspension is spray-dried, temperature is set as 105 DEG C~115 DEG C, finally obtains monodisperse micron Grade elastic microsphere powder.
Comparative example 2
1. 48.8g isophorone diisocyanate, 0.1g p-hydroxyanisole and 0.2g bismuth neodecanoate to be added to and be equipped with In the reaction flask of electric mixer, peristaltic pump and thermometer.Starting stirring, is warming up to 50 DEG C.9.7g polypropylene glycol is slowly added dropwise Reaction temperature is risen to 80 DEG C after dripping off by (molecular weight 2000), 25.9g polycaprolactone glycol (molecular weight 550), keeps the temperature 4 hours. 15.6g hydroxypropyl acrylate is eventually adding to be blocked to obtain urethane acrylate.
2. taking the urethane acrylate of the above-mentioned synthesis of 40g, 35g cyclohexyl methacrylate, 25g acrylic acid 17 is added Ester mixing, stirs to being completely dissolved, obtains mixed solution；
3. taking 0.5g neopelex, 1g TERGITOLTM15-S-20 and 100g water, which is mixed with, to be stablized Agent solution.
4. the mixed solution of step 2 and 0.5g peroxidating 2 ethyl hexanoic acid tert-pentyl ester to be added to the stabilizer of step 3 simultaneously In solution, it is dispersed and obtains pre- suspension；
5. pre- suspension is passed through nitrogen, 6h is kept the temperature after being warming up to 75 DEG C, reaction terminates, and obtains polymer suspension；
6. polymer suspension is spray-dried, temperature is set as 105 DEG C~115 DEG C, finally obtains monodisperse micron Grade elastic microsphere powder.
Comparative example 3
1. identical as the step 1 in embodiment 3；
2. taking the urethane acrylate of the above-mentioned synthesis of 20g, the mixing of 80g n-propyl is added, stirs to completely molten Solution, obtains mixed solution；
3. taking 1g ECOSURFTMEH-9 and 100g water are mixed with to obtain stabiliser solution.
4. the steady of step 3 is added in the mixed solution of step 2 and 0.5g benzoyl peroxide, 1g lauroyl peroxide simultaneously Determine in agent solution, is dispersed and obtains pre- suspension；
5. pre- suspension is passed through nitrogen, 6h is kept the temperature after being warming up to 75 DEG C, reaction terminates, and obtains polymer suspension；
6. polymer suspension is spray-dried, temperature is set as 105 DEG C~115 DEG C, finally obtains monodisperse micron Grade elastic microsphere powder.
Comparative example 4
1. identical as the step 1 in embodiment 3；
2. taking the urethane acrylate of the above-mentioned synthesis of 80g, the mixing of 20g n-propyl is added, stirs to completely molten Solution, obtains mixed solution；
3. taking 0.5g disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, 1.5g ECOSURFTMEH-9 and 100g water is mixed with to obtain Stabiliser solution.
4. the steady of step 3 is added in the mixed solution of step 2 and 0.5g benzoyl peroxide, 1g lauroyl peroxide simultaneously Determine in agent solution, is dispersed and obtains pre- suspension；
5. pre- suspension is passed through nitrogen, 6h is kept the temperature after being warming up to 75 DEG C, reaction terminates, and obtains polymer suspension；
6. polymer suspension is spray-dried, temperature is set as 105 DEG C~115 DEG C, finally obtains monodisperse micron Grade elastic microsphere powder.
The measurement of each physical property carries out by the following method in the present invention: (1) number-average molecular weight/weight average molecular weight utilizes gel Permeation chromatography (GPC) measures the molecular weight (number-average molecular weight/weight average molecular weight) of prepolymer.When carrying out GPC measurement, elution Liquid is THF, and temperature is 23 ± 2 DEG C.(2) average grain diameter and dispersibility using distilled water as mobile phase, by latex be added dropwise to In Britain LS-230Coulter laser light scattering test pond, the average grain diameter and dispersibility of polymer beads in latex are measured.(3) Using the rebound degree of ultra micro hardness meter measurement polymer microballoon.
Experimental product performance in embodiment 1-8 and comparative example 1-4, as shown in table 1.As seen from Table 1, work as polyurethane When the molecular weight of acrylate is greater than 5000 less than 10000, the rebound degree of stability of suspension favorable elasticity microballoon is high, in the middle may be used To adjust the proportion of stabilizer or initiator and monomer, so that the performance of lotion is optimal.Polyurethane acroleic acid in comparative example 1 The molecular weight of ester is less than 5000, and compared with embodiment 1-8, obtained polymer elasticity microballoon rebound degree is low；Gather in comparative example 2 The molecular weight of urethane acrylate is greater than 20000, and compared with embodiment 1-8, obtained polymer elasticity microballoon rebound degree is low； Urethane acrylate dosage is very few in comparative example 3, is lower than 30 parts, obtained polymer elasticity microballoon rebound degree is low；Comparison Urethane acrylate dosage is excessive in example 4, is higher than 60 parts, obtained polymer elasticity microballoon rebound degree is low.Illustrate this hair Bright polymer elasticity microballoon can be widely used in cosmetics and coating, increase elasticity and sense of touch.
The performance of the mono dispersed micrograde elastic microsphere powder of the present invention of table 1
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation, it is other it is any without departing from the spirit and principles of the present invention made by change, modification, substitution, combination and simplify, It should be equivalent substitute mode, be included within the scope of the present invention.

Claims (10)

1. a kind of mono dispersed micrograde elastic microsphere powder, which is characterized in that the microballoon powder is by urethane acrylate It is mixed to get prepolymer with vinyl monomer, is added after initiator and stabilizer and pre- suspension is prepared by free radical polymerization, it will Pre- suspension is passed through nitrogen, obtains polymer suspension after heating, polymer suspension is dried obtained；The polyurethane Acrylate is that polyalcohol is added dropwise in isocyanates, then is blocked to obtain by hydroxy acryl acid ester monomer.
2. mono dispersed micrograde elastic microsphere powder according to claim 1, which is characterized in that the polyalcohol is binary Alcohol, the dihydric alcohol are polypropylene glycol, polytetrahydrofuran diol, polyethylene glycol adipate, poly adipate succinic acid ester, gather oneself One or more of interior esterdiol, polycarbonate glycol.
3. mono dispersed micrograde elastic microsphere powder according to claim 1, which is characterized in that the isocyanates is benzene Dimethylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate or 4,4'- dicyclohexyl methyl hydride two One or more of isocyanates；The hydroxy acryl acid ester monomer is (methyl) hydroxy-ethyl acrylate, (methyl) acrylic acid One or more of hydroxypropyl acrylate, (methyl) hy-droxybutyl, caprolactone modification (methyl) acrylate.
4. mono dispersed micrograde elastic microsphere powder according to claim 1, which is characterized in that the vinyl monomer is (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) n-butyl acrylate, (first Base) cyclohexyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) decyl acrylate, (methyl) lauryl acrylate, (methyl) 17 ester of acrylic acid, (methyl) octadecyl acrylate, (methyl) Behenyl acrylate, in isobornyl (methyl) acrylate More than one.
5. mono dispersed micrograde elastic microsphere powder according to claim 1, which is characterized in that the stabilizer is ten Sodium dialkyl sulfate, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, cetyl diphenyl ether sodium disulfonate, sodium dioctylsuccinate, ten Glycol polyethers sodium sulphate, dodecyl sodium sulfate or neopelex, TRITONTMX-305、TERGITOLTM15-S- 20、TERGITOLTMTMN-100X、ECOSURFTMEH-9、TERGITOLTM26-L-9、ECOSURFTMOne or more of SA-15.
6. mono dispersed micrograde elastic microsphere powder according to claim 1, which is characterized in that the initiator is to have Machine peroxide and azo initiators.
7. mono dispersed micrograde elastic microsphere powder according to claim 6, which is characterized in that organic mistake Oxide be benzoyl peroxide, lauroyl peroxide, peroxidating neopentanoic acid tert-pentyl ester, peroxidating 2 ethyl hexanoic acid tert-pentyl ester or One or more of peroxidating 2 ethyl hexanoic acid tert-butyl ester；The azo initiators are azodiisobutyronitrile, azo two is different One or more of heptonitrile or azobisisovaleronitrile.
8. mono dispersed micrograde elastic microsphere powder according to claim 1, which is characterized in that the polyurethane acroleic acid The mass ratio of ester and vinyl monomer is (3~6): (4~7)；The mass ratio of the stabilizer and prepolymer is (0.1~1): 20；The mass ratio of the initiator and prepolymer is (0.5~3): 100；The equal molecule of the number of the urethane acrylate Amount is 5000~20000；The contents of ethylene of the urethane acrylate is 0.1~1mmol/g.
9. described in any item mono dispersed micrograde elastic microsphere raw powder's production technologies, feature exist according to claim 1~8 In comprising the following specific steps that:
S1. polyalcohol is added dropwise in isocyanates, is then blocked to obtain polyurethane third by hydroxy acryl acid ester monomer Olefin(e) acid ester；
S2. urethane acrylate and vinyl monomer mixing, stir to being completely dissolved, obtain mixed solution；
S3. the mixed solution of step S2 and initiator are added in stabiliser solution simultaneously, are dispersed and obtain pre- suspension；
S4. pre- suspension is passed through nitrogen, 4~8h is kept the temperature after being warming up to 50~80 DEG C, reaction terminates, and obtains polymer suspension Liquid；
S5. polymer suspension is dried at 105~115 DEG C, obtains mono dispersed micrograde elastic microsphere powder.
10. mono dispersed micrograde elastic microsphere powder answering in cosmetics or coating according to any one of claims 1 to 8 With.
CN201910267192.5A 2019-04-03 2019-04-03 A kind of mono dispersed micrograde elastic microsphere powder and its preparation method and application Withdrawn CN110041465A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910267192.5A CN110041465A (en) 2019-04-03 2019-04-03 A kind of mono dispersed micrograde elastic microsphere powder and its preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910267192.5A CN110041465A (en) 2019-04-03 2019-04-03 A kind of mono dispersed micrograde elastic microsphere powder and its preparation method and application

Publications (1)

Publication Number Publication Date
CN110041465A true CN110041465A (en) 2019-07-23

Family

ID=67275981

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910267192.5A Withdrawn CN110041465A (en) 2019-04-03 2019-04-03 A kind of mono dispersed micrograde elastic microsphere powder and its preparation method and application

Country Status (1)

Country Link
CN (1) CN110041465A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114272156A (en) * 2021-12-10 2022-04-05 广州融汇化妆品有限公司 Oil-removing fluffy washing-free hair drying spray and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4223114A (en) * 1977-09-13 1980-09-16 Bayer Aktiengesellschaft Process for the production of bead polymers
US20020193505A1 (en) * 2000-06-06 2002-12-19 Mckee Graham Edmund Preparation of microsuspension polymers useful as coating materials
CN105622857A (en) * 2016-04-01 2016-06-01 武汉大学 Preparation method of interpenetrating-network-structure water-based polyurethane nano composite material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4223114A (en) * 1977-09-13 1980-09-16 Bayer Aktiengesellschaft Process for the production of bead polymers
US20020193505A1 (en) * 2000-06-06 2002-12-19 Mckee Graham Edmund Preparation of microsuspension polymers useful as coating materials
CN105622857A (en) * 2016-04-01 2016-06-01 武汉大学 Preparation method of interpenetrating-network-structure water-based polyurethane nano composite material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
周凯军: "聚氨酯/丙烯酸酯热膨胀微球的制备与性能研究", 《塑料工业》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114272156A (en) * 2021-12-10 2022-04-05 广州融汇化妆品有限公司 Oil-removing fluffy washing-free hair drying spray and preparation method thereof
CN114272156B (en) * 2021-12-10 2023-06-16 广州融汇化妆品有限公司 Deoiling fluffy washing-free hair drying spray and preparation method thereof

Similar Documents

Publication Publication Date Title
CA1297489C (en) Process for producing low molecular weight, hydroxy functional (meth)acrylate polymers, their use for producing isocyanate terminal group-containing prepolymers as well as sealants and adhesives produced therefrom
CN1345900A (en) Levelling agent for surface paint
JP2016135877A (en) Irregular shaped particle
EP2640762A1 (en) Copolymers which can be obtained from urethane-based, polysiloxane-containing macromonomers, processes for the preparation thereof and their use
CN102675951A (en) Water-repellent modified association thickening agent and preparation method thereof
CN108586667A (en) A kind of preparation method and products thereof of the polyurethane-modified polyacrylate dispersion of resistance to water logging with resilient, crosslinked
CN109021161A (en) A kind of method that microchannel plate should synthesize GMA acrylic resin
CN104640890B (en) Multistage polymerization object and preparation method thereof as interground addition
CN109575191A (en) A kind of preparation method and application of super branched polyurethane/acrylate core-shell latex
WO2020068720A1 (en) Dual cure resins for additive manufacturing
CN102458632A (en) Branched polymer dispersants
AU2016222473B2 (en) Pigmented paint formulation with a phosphorus acid functionalized latex binder and an associative thickener
CN110041465A (en) A kind of mono dispersed micrograde elastic microsphere powder and its preparation method and application
JPS62246916A (en) Composite three-dimensional resin particle and its production
CN110483698A (en) A kind of aqueous polyurethane multiple emulsion and preparation method thereof
CN106519155B (en) The method for preparing high solids content soap-free polymerization object lotion based on semi-continuous charging method
CN106832201A (en) A kind of method for preparing monodisperse polymer microsphere in micro level at room temperature
CN105324457A (en) Hydrophilic thickener and cosmetic composition
EP3932962A1 (en) Aqueous polymer dispersion composition
CN108383939B (en) glycidyl methacrylate modified hydroxyl acrylic acid dispersoid and synthesis process thereof
CN115710340A (en) Hydrophobic monomer for thickening agent, preparation method and application
AU2014346940A1 (en) Catalyst compositions and methods of preparing them
EP1384734B1 (en) Particles of carboxylated polymer
JP2015172028A (en) cosmetic
JP2015166418A (en) thickening composition

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WW01 Invention patent application withdrawn after publication
WW01 Invention patent application withdrawn after publication

Application publication date: 20190723