CN107686563A - A kind of method and microballoon foaming agent that microballoon foaming agent is prepared using spray-on process - Google Patents
A kind of method and microballoon foaming agent that microballoon foaming agent is prepared using spray-on process Download PDFInfo
- Publication number
- CN107686563A CN107686563A CN201710706036.5A CN201710706036A CN107686563A CN 107686563 A CN107686563 A CN 107686563A CN 201710706036 A CN201710706036 A CN 201710706036A CN 107686563 A CN107686563 A CN 107686563A
- Authority
- CN
- China
- Prior art keywords
- foaming agent
- prepared
- spray
- microballoon foaming
- microballoon
- 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.)
- Pending
Links
Classifications
-
- 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
- C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
-
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/22—Expandable microspheres, e.g. Expancel®
-
- 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
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/06—Polystyrene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
It is proposed a kind of method that microballoon foaming agent is prepared using spray-on process, its technology point is that the thermoplastic resin solution of preparation is atomized into drop ditch re-evaporation removes solvent, after rapid condensation, drying are deposited on foaming agent surface, it is repeated in being heated after above step prepares sandwich construction, encapsulated blowing agent curing molding after resin softening, microballoon foaming agent is obtained through ball milling.Microballoon foaming agent is prepared using this method, not only equipment is simple compared with suspension polymerization, and technique is more environmentally friendly, and production cost is easily controlled, and production controllability is higher.
Description
Technical field
The present invention relates to foaming agent technical field, more particularly to a kind of method that microballoon foaming agent is prepared using spray-on process
And microballoon foaming agent.
Background technology
The foaming agent that heat-expandable microsphere includes the shell of thermoplastic resin and is encapsulated in shell, commonly referred to as heat is swollen for it
Swollen property micro-capsule.Thermoplastic resin generally includes vinylidene chloride based copolymer, acrylic copolymer and acrylate copolymer.
The foaming agent mainly used includes hydrocarbon, such as iso-butane and isopentane.Thermal expansion foam microspheres have excellent foam performance, excellent
Good solvent resistance, wearability, electrical insulating property, the advantages that good mechanical performance and nontoxic pollution-free, available for coating, spin
Knit, plastic processing, adhesive, sealing ring, synthetic leather, insulation, the field such as lightweighting materials.In such microballoon, foaming agent leads to
It is often the liquid that boiling temperature is not higher than thermoplastic polymer shell softening temperature.Once heating, foaming agent evaporates and increases internal pressure,
At the same time, housing softens, so as to cause the microballoon significantly to expand.
Expandable microspheres are prepared using suspension polymerization substantially both at home and abroad at present.Suspension polymerisation will be by that will include foaming agent and gather
The polymerizable compound for closing monomer is dispersed in incompatible liquid such as water and forms shell, and shell is to wrap up the thin layer form of interior foaming agent
Formed.In process for suspension polymerization, foaming agent and polymerizable compound including polymerisable monomer are by continuously stirring or adding
The stabilizer such as magnesium hydroxide or cataloid and keep suspended state.By suspension polymerisation, polymer can be formed
It is spherical.
US 20110123807 proposes a kind of preparation method of the thermal expansion type foam microspheres with core shell structure, with foaming
Agent is core, and long-chain crosslinking agent of the number-average molecular weight having using thermoplastic resin and between crosslink sites more than 500 is shell.Should
Method can increase the viscosity of monomer and blowing agent blends, prepare the thermal expansion type microballoon with homogeneous diameter.But propylene
The addition of esters of gallic acid long-chain crosslinking agent, adds the crosslink density in sheath polymers strand, improves the mechanical strength of shell,
But foam stabilizing temperature range is also reduced simultaneously.
US7931967B2 prepares a kind of thermal expansion type in the presence of polymerizable organo-silicon compound with suspension polymerization
Microballoon, shell composition includes polymerisable monomer copolymer and organo-silicon compound, by shell layer surface silicone functionalities to nothing
The adhesive force of machine particle, a certain amount of inorganic particulate is adhered to by chemical bond in microsphere surface, avoids foam microspheres particle from making
Caused agglomeration traits in standby process and foaming process.But cost of material is added using polymerizable organo-silicon compound, is influenceed
The polymerisation of acrylate monomer, the inorganic particulate of microsphere surface bonding influence the purity of microballoon.
Suspension polymerisation uses HTHP polymerization technique, but these preparation methods have the following disadvantages:Equipment investment is big, instead
High energy consumption is answered, polymerization exotherm easily makes the boiling vaporization of low boiling point hydrocarbon foaming agent under the high temperature conditions, is not easy processability stabilization
Foam microspheres and processing safety is low, environmental requirement is tight, and production cost is difficult to control.
The content of the invention
It is big that the equipment investment of microballoon foaming agent is prepared for current suspension polymerisation, energy consumption of reaction is high, gathers under the high temperature conditions
Closing heat release easily makes low-boiling foaming agent boiling vaporization, is not easy the stable foam microspheres of processability and processing safety is low, environmental protection
It is required that tight, the shortcomings that production cost be difficult to control, microballoon foaming agent is prepared using spray-on process it is an object of the invention to provide a kind of
Method and microballoon foaming agent, it has equipment simple, and technique is more environmentally friendly, and production cost is easily controlled, produce controllability
The advantages of higher.
To solve the above problems, the present invention uses following technical scheme：
A kind of method that microballoon foaming agent is prepared using spray-on process, is comprised the following steps：
（1）The preparation of resin emulsion：By acrylonitrile, acrylate monomer, emulsifying agent, bicarbonate and chain initiator in a solvent
It is well mixed, after vacuumizing deoxygenation, 60 ~ 240min is reacted at 25 ~ 40 DEG C, obtains resin emulsion；
（2）It is set to be dispersed into liquid little particle by ultrasonic wave in the showerhead using resin emulsion as spray solution, with vaporific shape
Formula sprays from shower nozzle；Solution after atomization uniformly falls on the undertaking body foaming agent of lower section, after curing process, with 15 DEG C/min's
Speed is cooled to room temperature, in the Surface coating base resin of foaming agent, obtains microballoon foaming agent.
Due to the method that microballoon foaming agent mainly uses HTHP in the prior art, equipment cost is high, and security
Relatively low, therefore, polymer emulsion is sprayed on the surface of foaming agent using a kind of spray-on process by invention of the invention, so as to form core
The microballoon foaming agent of shell structure, the technique of this method is simple, at normal temperatures and pressures i.e. can be achieved, without complexity equipment and instrument,
So as to reduce production cost and maintenance cost.
Polymer emulsion is coated in the surface of foaming agent using the method for spraying by the present invention, caused by once spraying
The content of polymer emulsion is less, thus the clad formed on foaming agent surface is also than relatively thin, or even there is also can not be complete
The situation of full encapsulated blowing agent, foaming agent can not be ensured in follow-up normal use, therefore, in preparation process, the step
（2）Repeat at least 2 ~ 8 times, so as to form complete cladding shell on foaming agent surface.
Due in spraying process, it is possible that the phenomenon that part enclosure is bonded together, therefore, in solidified forming
Afterwards, ball-milling treatment is carried out to microballoon foaming agent so that can be separated each other between foaming agent, ball-milling technology is to microballoon in the present invention
The performance impact of foaming agent is very big, if the degree of ball milling is inadequate, it is impossible to makes to separate each other between microballoon foaming agent, if ball milling
Excessively, then it may cause the broken of shell, and cause the failure of microballoon foaming agent, it is preferred that the technique of the ball-milling treatment is：
Ratio of grinding media to material is（2~5）：1；Ball-milling Time is 15-30min.
In order to simplify the technique of subsequent cure shaping, it is preferred that in step（1）In, the solvent is low boiling point solvent；Enter
One step is preferable, the low boiling point solvent be selected from butane, iso-butane, pentane, isopentane, neopentane, hexane, isohexane, heptane,
Isoheptane, at least one of octane, isooctane.
The sheathing material of expandable microspheres can be commonly used acrylate and acrylonitrile in the prior art in the present invention, its
In, the species of acrylate can be known to one of ordinary skill in the art, for example, the acrylate can be methacrylic acid
Methyl esters, methacrylic acid N, N- dimethylaminoethyl, n-BMA, Tert-butyl Methacrylate, methyl acrylate,
At least one of ethyl acrylate, 2- methyl methacrylates and ethyl 2-methacrylate.
The emulsifying agent is polyoxyethylene nonyl phenolic ether, polyoxyethylene nonyl phenolic ether sodium sulphate, lauryl sodium sulfate, dodecane
Base benzene sulfonic acid sodium salt, tween-20, tween-40, tween-60, span-20, span-40, span-60, OP-10, vinyl sulphur
At least one of sour sodium, sodium p styrene sulfonate, ALS.
Initiator refers to promote molecule chain extension, the compound of extension, initiator can make reaction system carry out chain extension and
Crosslinking, they have the characteristic group that can be chemically reacted with reaction system, and molecular weight is low, and reaction is active, and they can be extremely
Effectively adjust the reaction speed of reaction system.The chain initiator is ethylene glycol, propane diols, 1,4- butanediols, a contracting diethyl
Glycol, glycerine, trimethylolpropane, 1,4- cyclohexanediols, hydrogenated bisphenol A, α-allylin, glycidol pi-allyl
Ether, cumyl peroxide, sulphur.
The species of the foaming agent can be known to the field, such as organic foaming agent and inorganic foaming agent, it is preferred that institute
Foaming agent is stated as azodiisobutyronitrile, azodicarbonamide, N, N- dinitrosopentamethylene tetramines and C4-C6 aliphatic hydrocarbon
At least one of class compound.
Heretofore described resin emulsion uses auto injection technique, and the technique of the auto injection is：Flow：30~45μ
L/min；Distribute the time：90~110s；Distribute liquid measure：40~60μL；Interval time：0.1min；Syringe bore：4.25mm.
The present invention does not have special requirement to curing process, can often know for the art personnel, for example, described
The temperature of curing process is 50-60 DEG C, and the time of curing process is 5 ~ 30min.
A kind of microballoon foaming agent, is prepared according to above-mentioned preparation method.
The particle diameter of the microballoon foaming agent is 2 ~ 15 microns, and expansion multiplying power is 3.8 ~ 5.9 times.
A kind of method and microballoon foaming agent that microballoon foaming agent is prepared using spray-on process of the present invention, compared with prior art,
The characteristics of it is protruded and excellent effect are：
The method that the present invention prepares microballoon foaming agent using spray-on process, drop ditch is atomized into again by the thermoplastic resin solution of preparation
Evaporation of solvent, rapid condensation, after drying and being deposited on foaming agent surface, being repeated in above step, to prepare sandwich construction laggard
Row heating, encapsulated blowing agent curing molding after resin softening, microballoon foaming agent is obtained through ball milling.Microballoon foaming is prepared using this method
Agent, not only equipment is simple compared with suspension polymerization, and technique is more environmentally friendly, and production cost is easily controlled, and production controllability is more
It is high.
Embodiment
Below by way of embodiment, the present invention is described in further detail, but this should not be interpreted as to the present invention
Scope be only limitted to following example.In the case where not departing from above method thought of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
A kind of method that microballoon foaming agent is prepared using spray-on process, is comprised the following steps：
（1）The preparation of resin emulsion：By acrylonitrile, methyl methacrylate, lauryl sodium sulfate, bicarbonate and a contracting two
Ethylene glycol is well mixed in butane, after vacuumizing deoxygenation, is reacted 60min at 25 DEG C, is obtained resin emulsion, resin emulsion is adopted
With auto injection technique, the technique of the auto injection is：Flow：30μL/min；Distribute the time：90s；Distribute liquid measure：40μL；
Interval time：0.1min；Syringe bore：4.25mm.
（2）It is set to be dispersed into liquid little particle by ultrasonic wave in the showerhead using resin emulsion as spray solution, with mist
Shape form sprays from shower nozzle；Solution after atomization uniformly falls on the undertaking body azodiisobutyronitrile of lower section, carries out curing process,
Temperature is 50 DEG C, and the time of curing process is 5min；After solidified forming, ball milling described in ball-milling treatment is carried out to microballoon foaming agent
The technique of processing is：Ratio of grinding media to material is 2：1；Ball-milling Time is 30min.Room temperature is cooled to 15 DEG C/min speed, in azo two
The Surface coating base resin of isobutyronitrile, repeat at least 2 times, so as to formed on foaming agent surface complete cladding shell obtain it is micro-
Ball foaming agent.The particle diameter of the microballoon foaming agent is 5 microns, and expansion multiplying power is 4.9 times.
Embodiment 2
A kind of method that microballoon foaming agent is prepared using spray-on process, is comprised the following steps：
（1）The preparation of resin emulsion：By acrylonitrile, methyl methacrylate, lauryl sodium sulfate, bicarbonate and a contracting two
Ethylene glycol is well mixed in butane, after vacuumizing deoxygenation, is reacted 65min at 26 DEG C, is obtained resin emulsion；Resin emulsion is adopted
With auto injection technique, the technique of the auto injection is：Flow：31μL/min；Distribute the time：91s；Distribute liquid measure：41μL；
Interval time：0.1min；Syringe bore：4.25mm.
（2）It is set to be dispersed into liquid little particle by ultrasonic wave in the showerhead using resin emulsion as spray solution, with mist
Shape form sprays from shower nozzle；Solution after atomization uniformly falls on the undertaking body azodiisobutyronitrile of lower section, carries out curing process,
Temperature is 60 DEG C, and the time of curing process is 6min；After solidified forming, ball milling described in ball-milling treatment is carried out to microballoon foaming agent
The technique of processing is：Ratio of grinding media to material is 3：1；Ball-milling Time is 20min.Room temperature is cooled to 15 DEG C/min speed, in azo two
The Surface coating base resin of isobutyronitrile, repeat at least 3 times, so as to formed on foaming agent surface complete cladding shell obtain it is micro-
Ball foaming agent.
The particle diameter of the microballoon foaming agent is 5 microns, and expansion multiplying power is 4 times.
Embodiment 3
A kind of method that microballoon foaming agent is prepared using spray-on process, is comprised the following steps：
（1）The preparation of resin emulsion：By acrylonitrile, n-BMA, span-20, bicarbonate and glycerine new
It is well mixed in pentane, after vacuumizing deoxygenation, reacts 80min at 26 DEG C, obtain resin emulsion；Resin emulsion uses to enter automatically
Sampling technology, the technique of the auto injection are：Flow：35μL/min；Distribute the time：92s；Distribute liquid measure：42μL；During interval
Between：0.1min；Syringe bore：4.25mm.
（2）It is set to be dispersed into liquid little particle by ultrasonic wave in the showerhead using resin emulsion as spray solution, with mist
Shape form sprays from shower nozzle；Solution after atomization uniformly falls on the undertaking body azodicarbonamide of lower section, carries out curing process,
Temperature is 55 DEG C, and the time of curing process is 8min；After solidified forming, ball milling described in ball-milling treatment is carried out to microballoon foaming agent
The technique of processing is：Ratio of grinding media to material is 4：1；Ball-milling Time is 15min.Room temperature is cooled to 15 DEG C/min speed, in azo two
The Surface coating base resin of formamide, repeat at least 4 times, so as to form complete cladding shell on azodicarbonamide surface
Obtain microballoon foaming agent.The particle diameter of the microballoon foaming agent is 4 microns, and expansion multiplying power is 5 times.
Embodiment 4
A kind of method that microballoon foaming agent is prepared using spray-on process, is comprised the following steps：
（1）The preparation of resin emulsion：By acrylonitrile, n-BMA, span-20, bicarbonate and glycerine new
It is well mixed in pentane, after vacuumizing deoxygenation, reacts 200min at 36 DEG C, obtain resin emulsion；Resin emulsion is using automatic
Enter sampling technology, the technique of the auto injection is：Flow：33μL/min；Distribute the time：93s；Distribute liquid measure：43μL；During interval
Between：0.1min；Syringe bore：4.25mm.
（2）It is set to be dispersed into liquid little particle by ultrasonic wave in the showerhead using resin emulsion as spray solution, with mist
Shape form sprays from shower nozzle；Solution after atomization uniformly falls on the undertaking body azodicarbonamide of lower section, carries out curing process,
Temperature is 60 DEG C, and the time of curing process is 24min；After solidified forming, ball described in ball-milling treatment is carried out to microballoon foaming agent
Grinding the technique handled is：Ratio of grinding media to material is 4：1；Ball-milling Time is 15min.Room temperature is cooled to 15 DEG C/min speed, in azo
The Surface coating base resin of diformamide, repeat at least 6 times, it is outer so as to form complete cladding on azodicarbonamide surface
Shell obtains microballoon foaming agent.
The particle diameter of the microballoon foaming agent is 5 microns, and expansion multiplying power is 3.9 times.
Embodiment 5
A kind of method that microballoon foaming agent is prepared using spray-on process, is comprised the following steps：
（1）The preparation of resin emulsion：By acrylonitrile, methyl methacrylate, lauryl sodium sulfate, bicarbonate and a contracting two
Ethylene glycol is well mixed in butane, after vacuumizing deoxygenation, is reacted 200min at 36 DEG C, is obtained resin emulsion；Resin emulsion
Using auto injection technique, the technique of the auto injection is：Flow：36μL/min；Distribute the time：96s；Distribute liquid measure：48μ
L；Interval time：0.1min；Syringe bore：4.25mm.
（2）It is set to be dispersed into liquid little particle by ultrasonic wave in the showerhead using resin emulsion as spray solution, with mist
Shape form sprays from shower nozzle；Solution after atomization uniformly falls on the undertaking body foaming agent of lower section, carries out curing process, and temperature is
50 DEG C, the time of curing process is 24min；After solidified forming, ball-milling treatment described in ball-milling treatment is carried out to microballoon foaming agent
Technique be：Ratio of grinding media to material is 5：1；Ball-milling Time is 15min.Room temperature is cooled to 15 DEG C/min speed, in the table of foaming agent
Bread covers base resin, repeats at least 6 times, and microballoon foaming agent is obtained so as to form complete cladding shell on foaming agent surface.
The particle diameter of the microballoon foaming agent is 10 microns, and expansion multiplying power is 3.8 times.
The microballoon foaming agent that embodiment 1-5 in the present invention is obtained is used for PS foaming, with uniform abscess and stably
Density, testing result see the table below 1.
Table 1:
Claims (10)
- A kind of 1. method that microballoon foaming agent is prepared using spray-on process, it is characterised in that comprise the following steps：（1）The preparation of resin emulsion：By acrylonitrile, acrylate monomer, emulsifying agent, bicarbonate and chain initiator in a solvent It is well mixed, after vacuumizing deoxygenation, 60 ~ 240min is reacted at 25 ~ 40 DEG C, obtains resin emulsion；（2）It is set to be dispersed into liquid little particle by ultrasonic wave in the showerhead using resin emulsion as spray solution, with vaporific shape Formula sprays from shower nozzle；Solution after atomization uniformly falls on the undertaking body foaming agent of lower section, after curing process, with 15 DEG C/min's Speed is cooled to room temperature, in the Surface coating base resin of foaming agent, obtains microballoon foaming agent.
- 2. the method according to claim 1 that microballoon foaming agent is prepared using spray-on process, it is characterised in that in preparation process In, the step（2）Repeat at least 2 ~ 8 times.
- 3. the method according to claim 1 that microballoon foaming agent is prepared using spray-on process, it is characterised in that curing process Afterwards, ball-milling treatment also is carried out to microballoon foaming agent；The technique of the ball-milling treatment is：Ratio of grinding media to material is（2~5）：1；Ball-milling Time is 15-300min.
- 4. the method according to claim 1 that microballoon foaming agent is prepared using spray-on process, it is characterised in that in step（1） In, the solvent is low boiling point solvent；The low boiling point solvent be selected from butane, iso-butane, pentane, isopentane, neopentane, hexane, isohexane, heptane, isoheptane, At least one of octane, isooctane.
- 5. the method according to claim 1 that microballoon foaming agent is prepared using spray-on process, it is characterised in that in step（1） In, the acrylate monomer is methyl methacrylate, methacrylic acid N, N- dimethylaminoethyl, the positive fourth of methacrylic acid Ester, Tert-butyl Methacrylate, methyl acrylate, ethyl acrylate, 2- methyl methacrylates and ethyl 2-methacrylate At least one of.
- 6. the method according to claim 1 that microballoon foaming agent is prepared using spray-on process, it is characterised in that in step（2） In, the foaming agent is selected from azodiisobutyronitrile, azodicarbonamide, N, N- dinitrosopentamethylene tetramines and C4-C6's At least one of aliphatic hydrocarbon compound.
- 7. the method according to claim 1 that microballoon foaming agent is prepared using spray-on process, it is characterised in that the resin breast Liquid uses auto injection technique, and the technique of the auto injection is：Flow：30~45μL/min；Distribute the time：90~110s；Point With liquid measure：40~60μL；Interval time：0.1min；Syringe bore：4.25mm.
- 8. the method according to claim 1 that microballoon foaming agent is prepared using spray-on process, it is characterised in that at the solidification The temperature of reason is 50-60 DEG C, and the time of curing process is 5 ~ 30min.
- 9. a kind of microballoon foaming agent, it is characterised in that the preparation method according to any one in claim 1 ~ 8 is prepared into Arrive.
- 10. microballoon foaming agent according to claim 9, it is characterised in that the particle diameter of the microballoon foaming agent is 2 ~ 15 micro- Rice, expansion multiplying power are 3.8 ~ 5.9 times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710706036.5A CN107686563A (en) | 2017-08-17 | 2017-08-17 | A kind of method and microballoon foaming agent that microballoon foaming agent is prepared using spray-on process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710706036.5A CN107686563A (en) | 2017-08-17 | 2017-08-17 | A kind of method and microballoon foaming agent that microballoon foaming agent is prepared using spray-on process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107686563A true CN107686563A (en) | 2018-02-13 |
Family
ID=61153391
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710706036.5A Pending CN107686563A (en) | 2017-08-17 | 2017-08-17 | A kind of method and microballoon foaming agent that microballoon foaming agent is prepared using spray-on process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107686563A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109679249A (en) * | 2018-12-30 | 2019-04-26 | 安徽科居新材料科技有限公司 | PVC wood plastic composite material and preparation method thereof |
| CN109721888A (en) * | 2018-12-30 | 2019-05-07 | 安徽科居新材料科技有限公司 | Wood plastic composite and preparation method thereof |
| CN109734953A (en) * | 2018-12-30 | 2019-05-10 | 安徽科居新材料科技有限公司 | PVC wood plastic composite material foaming agent and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106432781A (en) * | 2016-09-18 | 2017-02-22 | 三明市锦浪新材料科技有限公司 | Thermal expansion microcapsule, method for preparing same and application of thermal expansion microcapsule |
| CN107022095A (en) * | 2017-04-27 | 2017-08-08 | 东北大学 | A kind of method that utilization spray-on process prepares metal organic framework film |
-
2017
- 2017-08-17 CN CN201710706036.5A patent/CN107686563A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106432781A (en) * | 2016-09-18 | 2017-02-22 | 三明市锦浪新材料科技有限公司 | Thermal expansion microcapsule, method for preparing same and application of thermal expansion microcapsule |
| CN107022095A (en) * | 2017-04-27 | 2017-08-08 | 东北大学 | A kind of method that utilization spray-on process prepares metal organic framework film |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109679249A (en) * | 2018-12-30 | 2019-04-26 | 安徽科居新材料科技有限公司 | PVC wood plastic composite material and preparation method thereof |
| CN109721888A (en) * | 2018-12-30 | 2019-05-07 | 安徽科居新材料科技有限公司 | Wood plastic composite and preparation method thereof |
| CN109734953A (en) * | 2018-12-30 | 2019-05-10 | 安徽科居新材料科技有限公司 | PVC wood plastic composite material foaming agent and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107686563A (en) | A kind of method and microballoon foaming agent that microballoon foaming agent is prepared using spray-on process | |
| CN101306341B (en) | Phase-change accumulation energy microcapsule prepared by interfacial polymerization method and its method | |
| CN103497617B (en) | A kind of preparation method of self-emulsifying cation epoxy emulsion | |
| CN105367698B (en) | A kind of elastic water-proof emulsion | |
| CN109847664B (en) | Conductive thermal expansion type microcapsule and preparation method thereof | |
| CN106432781A (en) | Thermal expansion microcapsule, method for preparing same and application of thermal expansion microcapsule | |
| CN105148810B (en) | A kind of preparation method of composite balls | |
| CN105924569B (en) | A kind of preparation method of multinuclear coated complex microsphere | |
| CN104232014B (en) | A kind of underfill | |
| CN105504115B (en) | Eliminate the microcapsule method in situ that carbon black or graphite inhibit effect in Polystyrene heat insulation material synthesis | |
| CN1927444B (en) | Ureaformaldehyde resin bilaminar membrane coating epoxy resin microcapsule and preparing method thereof | |
| CN104744644A (en) | Organic-inorganic compound modified waterborne acrylic epoxy ester resin and preparation method thereof | |
| CN106189092A (en) | A kind of fiber reinforcement flame-retarded light high-strength composite material and preparation method thereof | |
| CN112341556A (en) | Preparation method of easy-demoulding polyvinyl chloride paste resin | |
| CN114369413A (en) | Root-puncture-resistant quick-setting spray rubber asphalt waterproof coating, and preparation method and application thereof | |
| CN114605845A (en) | Microcapsule controllable curing cold-mix epoxy asphalt and preparation method and application thereof | |
| CN106732217B (en) | A kind of preparation method of polymer microballoon | |
| CN105907290A (en) | Environment-friendly emulsion type water-based ultraviolet-curing plastic coating and preparation method thereof | |
| Yan et al. | Preparation and curing behavior of latent 2‐PhIm‐PS microcapsule curing agent for epoxy resin | |
| CN105859935A (en) | Preparation method of sponge polymer microspheres with internal having three-dimensional network structure | |
| CN105585658A (en) | Normal-temperature self-crosslinking fluorine-containing acrylate emulsion for woodware and preparation method thereof | |
| CN107337750B (en) | A kind of expandable poly-styrene and preparation method thereof | |
| CN113214795A (en) | Preparation method of ionic liquid phase-change microcapsule | |
| CN103788663B (en) | A kind of high-performance polymer spray film water-proofing material and preparation method thereof | |
| CN101580592B (en) | Water-based method for preparing organic silicon resin |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180213 |