CN106832110A - There is microspheres composition of foam performance and preparation method thereof at low temperature - Google Patents
There is microspheres composition of foam performance and preparation method thereof at low temperature Download PDFInfo
- Publication number
- CN106832110A CN106832110A CN201710042534.4A CN201710042534A CN106832110A CN 106832110 A CN106832110 A CN 106832110A CN 201710042534 A CN201710042534 A CN 201710042534A CN 106832110 A CN106832110 A CN 106832110A
- Authority
- CN
- China
- Prior art keywords
- low temperature
- foam performance
- monomer
- microspheres
- foaming agent
- 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
- 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
- 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
- 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
- C08J9/16—Making expandable particles
- C08J9/20—Making expandable particles by suspension polymerisation in the presence of the blowing agent
-
- 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
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
-
- 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
- C08J2333/00—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/18—Homopolymers or copolymers of nitriles
- C08J2333/20—Homopolymers or copolymers of acrylonitrile
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
The invention provides a kind of microspheres composition with foam performance at low temperature, it is made up of ethylenically unsaturated monomer and foaming agent, wherein, the ethylenically unsaturated monomer includes following component：Acrylonitrile, acrylic ester monomer and monomer containing polar end.It is of the invention that vinylidene of the prior art is mainly replaced with acrylic ester monomer, obtain with relatively low Tstart(70~90 DEG C) and compared with the heat-expandable microsphere of high expansion function, and add containing polar end ethylenically unsaturated monomer, improve dispersiveness of the microballoon in water, reach expected purpose of the present invention.
Description
Technical field
The present invention relates to a kind of microspheres composition with foam performance and preparation method thereof at low temperature, belong to
Technical field of polymer materials.
Background technology
The thermoplastic microspheres of thermal expansion are a kind of main by with thermoplastic polymer as shell and the tool that is constituted for core of foaming agent
There is the microsphere of core shell structure.In this kind of microballoon, bulking substances are generally not higher than the soft of thermoplastic polymer shell with boiling point
Change the liquid of temperature.In a heated condition, swelling agent gasification, internal pressure increase, while thermoplastic polymer (shell) softens, it is micro-
Ball substantially expands.Microballoon starts temperature referred to as T during expansionstart, reach temperature referred to as T during maximum swellingmax。
In some application fields, for example：Papermaking, ink printing etc., user wishes the thermal expansivity that supplier is provided
Microballoon has relatively low Tstart and swelliong power higher, and requires that microballoon has excellent dispersiveness in the slurry.
At present, temperature is risen in order to reduce microballoon, it is proposed that be incorporated into microballoon using vinylidene chloride as polymerized monomer
Shell in, but substantial amounts of halogen monomer is remained in this kind of microballoon, environment is polluted, and the microballoon chemically-resistant
Medicine and dispersiveness are poor.
Meanwhile, in order to improve the dispersiveness of microballoon, generally by monomer of the resin microsphere surface insertion containing polarity.
Propose for polar monomer SSS to be incorporated into microsphere surface in patent CN102746454A, it is microballoon to be effectively improved
Dispersiveness, but with the T of heat-expandable microsphere obtained in the methodstartIt is higher, limit its application in some fields.
The content of the invention
For above-mentioned technical problem of the prior art, the invention provides a kind of not halogen-containing and with relatively low
TstartThe preparation method of (typically at 70~90 DEG C), preferably dispersiveness and the heat-expandable microsphere compared with highly expanded ability.
The present invention is achieved by the following technical solutions：
In a first aspect, the invention provides a kind of microspheres composition with foam performance at low temperature, by alkene
Category unsaturated monomer and foaming agent composition, wherein, the ethylenically unsaturated monomer includes the following component of percentage：
Acrylonitrile：30~90%；
Acrylic ester monomer：9.9~60%；
Monomer containing polar end 0.1~10%.
In addition, crosslinking agent, initiator, dispersion stabilizer and/or stably dispersing are also included in raw material of the invention
The auxiliary agents such as auxiliary agent.
It is adapted to crosslinking agent of the invention to be not particularly limited, can selects to contain a kind of, two or more crosslinking
The compound of functional group, for example：Divinylbenzene, ethylene glycol two (methyl) acrylate, two (ethylene glycol) two (methyl) propylene
Acid esters, three (ethylene glycol) two (methyl) acrylate, propane diols two (methyl) acrylate, BDO two (methyl) propylene
Acid esters, 1,6-HD two (methyl) acrylate, glycerine two (methyl) acrylate, neopentyl glycol two (methyl) acrylic acid
Ester, 1,6-HD two (methyl) acrylate, 1,9- nonanediols two (methyl) acrylate, 1,10- decanediols two (methyl)
Acrylate, Glycerin three (methyl) acrylate, three (methyl) acrylate, pentaerythritols, four (methyl) acrylic acid seasons
Doutrate, six (methyl) acrylate, pentaerythritols, three (methyl) acrylic acid the trihydroxymethylpropanyl esters, (first of three butanediol two
Base) acrylate, PEG#200 bis- (methyl) acrylic acid, PEG#400 bis- (methyl) acrylate, PEG#600 bis- (methyl) propylene
Acid esters, 3 acrylic acid epoxide diol mono-acrylate, three acyl group formals, Triallyl isocyanurate, divinyl ether, second
Divinyl ether, diethylene glycol divinyl ether, triethyleneglycol divinylether, TEG divinyl ether, triolefin
Propyl group formal three (methyl) acrylate etc..
For the consumption of above-mentioned crosslinking agent be for preparing the 0.1 of the monomer gross mass of thermoplastic polymer (shell)~
10wt%, further preferred consumption is 1~5wt% for preparing the total monomer weight of thermoplastic polymer (shell), more excellent
The consumption of choosing is 1~3wt% for preparing the total monomer weight of thermoplastic polymer (shell).
It is adapted to initiator of the invention to be not particularly limited, for initiator (such as organic peroxide of radical polymerization
Or azo compound etc.) be suitable for the present invention, specific initiator be selected from one kind in following compounds, two kinds or two kinds with
On be used in mixed way, for example：Peroxidating tin dilaurate, the capric acid of peroxidating two, tert-butyl hydroperoxide trimethylace tonitric ester, tert-butyl group mistake
Laurate, tert butyl peroxy benzoate, tert-butyl hydroperoxide neodecanoic acid ester, tertiary hexyl new decanoate ester peroxide, 1- rings
Hexyl -1- Methylethyls new decanoate ester peroxide, the hydroperoxidation tert-butyl ester, cumene hydroperoxide, ethene cumene peroxide, peroxide
Change the organic peroxides such as decoyl, lauroyl peroxide；2,2 '-azo double (2,4- methyl pentane nitriles), dimethyl 2,2 '-azo
Double (2 Methylpropionic acid esters), 2,2 '-azodiisobutyronitrile, 2,2 '-azo double [2- methyl-N- (2- ethoxys)-lactams], 2,
The azo-compounds such as 2 '-azo double (4- methoxyl group -2,4- methyl pentane nitriles), 1,1 '-azo double (hexamethylene -1- nitriles).
For the consumption of above-mentioned initiator be for preparing the 0.1 of the monomer gross mass of thermoplastic polymer (shell)~
10wt%, further preferred consumption is 0.5~8wt% for preparing the total monomer weight of thermoplastic polymer (shell), more
Preferred consumption is 0.3~7wt% for preparing the total monomer weight of thermoplastic polymer (shell).
It is preferably set to be carried out in the aqueous dispersion medium containing dispersion stabilizer and/or stably dispersing auxiliary agent in the present invention
Suspension polymerisation.For the usage amount of described aqueous dispersion medium, there is no particular limitation, equivalent to aqueous point of 100 weight portions
Dispersion media.
Wherein described dispersion stabilizer, can be cataloid, gel calcium carbonate, magnesium hydroxide, calcium phosphate, hydrogen
Aluminum oxide, iron hydroxide, calcium sulfate, sodium sulphate, calcium oxalate, calcium carbonate, barium carbonate, magnesium carbonate or/and aluminum hydroxide sol etc..
The consumption of dispersion stabilizer is preferably 0.1~20wt% of polymerizable components (can polycondensation monomer total amount) gross weight.
Above-mentioned stably dispersing auxiliary agent is further preferential：It is the condensation product of diethanol amine and aliphatic dicarboxylic acid, gelatin, poly-
The stably dispersing auxiliary agent of the polymer electrolytes such as vinylpyrrolidone, methylcellulose, PEO, polyvinyl alcohol, chlorination alkyl
The anion surfactants such as the cationic surfactant such as Trimethylamine or chlorination dialkyl dimethyl ammonium, sodium alkyl sulfate,
Zwitterionic surfactants such as alkyl dimethyl aminoacetic acid glycine betaine, alkyl dihydroxyethyl aminoacetic acid glycine betaine etc. are each
Plant emulsifying agent.The consumption of stably dispersing auxiliary agent is preferably 0.001~2.0wt% of polymerizable components gross mass.
Entering for dispersiveness can be realized with attaching surface modifying agent in the appearance of heat-expandable microsphere provided by the present invention
One step is improved or mobility further improves.
Accompanying surface modifier (can contain two for one or more in organic system or inorganic system's modifying agent
Kind) mixture.
The organic system modifying agent, for example：Magnesium stearate, calcium stearate, stearic acid alkene, barium stearate, lithium stearate etc.
Metal soap：Tissuemat E, laurate acid amide, nutmeg acid acid amides, palm fibre put the conjunction such as sour acid amides, stearoylketene amine, hardened castor oil
Into wax class；Polyacrylamide, polyimides, nylon, polymethyl methacrylate, polyethylene or polytetrafluoroethylene (PTFE) etc..
Inorganic system's modifying agent, for example：Talcum, mica, bentonite, sericite, carbon black, curing aluminium, tungsten disulfide,
Fluorographite, calcirm-fluoride, boron nitride, silica, aluminum oxide, mica, calcium carbonate, calcium hydroxide, calcium phosphate, magnesium hydroxide,
Magnesium phosphate, barium sulfate, zinc oxide, ceramic bead or crystal pearl etc..
Adhesion amount (being attached to heat-expandable microsphere surface) for the surface modifier is not particularly limited.But if
It is 100 weights with the gross mass of unattached heat-expandable microsphere in view of can fully play function of surface modifier etc.
Amount number meter, the adhesion amount of the surface modifier is 0.1~95wt%, preferably 0.5~60wt%, further preferential 5~
50wt%, most preferably 8~30wt%.
The attachment of surface modifier can be carried out by mixing unattached heat-expandable microsphere and surface modifier.For
Mixing is not particularly limited, and can be carried out in the container with agitating device.In addition can also carry out it is common shake or stirring
Powder mixer.Used as powder mixer, can for example enumerate zonate frond type mixer, vertical spin type mixer etc. can
Shake the powder mixer of stirring or stirring.Alternatively, it is also possible to using in recent years by the efficiency that combines agitating device more
Multi-functional powder mixer high is super mixer and high-speed mixer, SV mixers etc..
Preferably, the acrylic ester monomer be methyl methacrylate and methyl acrylate in one kind or
Two kinds.
Preferably, the monomer containing polar end is the one kind or two in styrene sulfonic acid and SSS
Kind.
Preferably, it 100% is calculating benchmark to be by thermo-expandable microspheres weight, and the percetage by weight of foaming agent is
15~50%.
Preferably, the foaming agent is C4-C6Aliphatic hydrocarbon compound.
Preferably, the foaming agent is C4-C5Straight chain, side chain or ring-type saturated hydrocarbons compound.
Preferably, the foaming agent is selected from least one in iso-butane, isopentane, neopentane.
Second aspect, present invention also offers a kind of microspheres group with foam performance at low temperature as the aforementioned
The preparation method of compound, comprises the following steps：It is to mix acrylonitrile, acrylic ester monomer, monomer containing polar end, foaming agent
Afterwards, by suspension polymerisation, the microspheres composition with foam performance at low temperature is obtained.
Depending on can be according to the species of initiator used as described suspension polymerization temperatures, the suspension that the present invention recommends gathers
It is 40~100 DEG C to close temperature, and preferred suspension polymerization temperatures are 45~90 DEG C, more preferably 50~85 DEG C.
For polymerization initial stage pressure, preferential meter pressure is 0~5.0MPa, and then preferably 0.1~3.0MPa, particularly preferably
0.2~2.0PMa.
When the polymerisation is essentially complete, the microballoon of water paste or dispersion can be obtained, they can in statu quo be used or logical
Cross any conventional method (such as bed filter, press filtration, leaf filter, band filter or centrifugation are dehydrated) and obtain so-called wet cake.And
Can by any conventional method (for example spray drying, support drying, tunnel drying, Rotary drying, drum dried, aeration-drying,
Turbo shelf drying, disk drying or fluidized bed drying etc.) microballoon is dried.
In another optimal technical scheme of the invention, acrylamide monomers, propylene can be selected containing polar end monomer
The unsaturated monocarboxylics such as acid, methacrylic acid, ethylacrylic acid, crotonic acid, or be the dicarboxylic acids such as maleic acid, itaconic acid, its
In at least one preferably in acrylic acid and methacrylic acid, or both be used in conjunction with.
The consumption containing polar end monomer is for preparing the 1 of the monomer gross mass of thermoplastic polymer (shell) for more than
~10wt%, further preferred consumption is 2~8wt% for preparing the monomer gross mass of thermoplastic polymer (shell), more
Preferential consumption is 3~7wt% for preparing the monomer gross mass of thermoplastic polymer (shell).
Compared with prior art, the present invention has following beneficial effect：
It is of the invention main that vinylidene of the prior art is replaced with acrylic ester monomer, obtain with compared with
Low Tstart(70~90 DEG C) and compared with the heat-expandable microsphere of high expansion function, and add containing polar end ethylenically unsaturated monomer,
Dispersiveness of the microballoon in water is improve, expected purpose of the present invention is reached.
Brief description of the drawings
The detailed description made to non-limiting example with reference to the following drawings by reading, further feature of the invention,
Objects and advantages will become more apparent upon：
Fig. 1 is the stereoscan photograph of microspheres composition prepared by the present invention.
Specific embodiment
With reference to specific embodiment, the present invention is described in detail.Following examples will be helpful to the technology of this area
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that to the ordinary skill of this area
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection domain.
Below by embodiment, the present invention is further elaborated.In listed embodiment, unless otherwise indicated, embodiment
In all fractions and percentage refer to fraction and percentage by weight, and the analysis of heat-expandable microsphere uses following method
And instrument：
(1) particle size distribution profiles analysis：
The particle diameter distribution of microballoon is the particle diameter distribution sub-laser diffraction analyzer produced by Bekman coulter companies
LS13320 is measured.Average grain diameter is measured as volume average particle size, and particle diameter distribution is calculated as C.V. values (the quasi- deviation of table/average straight
Footpath) × 100.
(2) foam characteristics analysis：
The characteristic of heat-expandable microsphere is surveyed by the special mechanical analyzer TMA Q-400 that TA Instrument companies produce
Amount.By the 1.0mg heat-expandable microsphere samples accommodated in the aluminium dish of diameter 6.7mm and depth 4.5mm, the aluminium dish diameter
The aluminium dish sealing of 6.5mm and depth 4.0mm.According to TMA expanding probe types, sample temperature with the heating rate of 50 DEG C/min from
Environment temperature is increased to 230 DEG C, and applies the power of 0.5N by probe, and analysis is carried out by measuring probe vertical displacement.
Expansion initial temperature (Tstart)：Probe displacement starts the temperature (DEG C) during increase；
Foaming maximum temperature (Tmax)：Probe displacement reaches the temperature (DEG C) during maximum；
Maximum foaming displacement (Dmax)：Probe displacement reaches the displacement (um) that maximum is.
Embodiment 1
The present embodiment is related to a kind of preparation method of the microspheres composition with foam performance at low temperature, including
Following steps：
First, by mixing 80g acrylonitrile, 20g methyl methacrylates, 50g methyl acrylates, 1.2g styrene sulfonic acids
Sodium, 0.8g trimethylol-propane trimethacrylates, 4g benzoyl peroxides and 50g iso-butanes obtain the oil of suspension polymerisation
Phase；
2nd, 280g deionized waters, 30g NaOH, 40g sodium chloride and 0.2g dodecyl sulphur are added in No. 1 beaker
Sour sodium fully dissolves；280g deionized waters, 85g Magnesium dichloride hexahydrates, 30g sodium chloride, the Asia of 0.01g are added in No. 2 flasks
Sodium nitrate fully dissolves；First the solution in No. 1 beaker is poured into the 2.5L there-necked flasks with agitating paddle, Ran Hou
Under the stirring of 1200rpm rotating speeds, then to the solution being slowly added in the there-necked flask in No. 2 flasks.15 are sufficiently stirred for after adding again
Minute, obtain the water phase of suspension polymerisation；
3rd, oil phase and water phase are disperseed by stirring with homogeneous mixer 2 minutes under 7000rpm, so as to prepare suspension
Solution.Aaerosol solution is injected in 1L autoclaves at once, leads to nitrogen protection, and to the supercharging of reactor reaching 0.3MPa
Initial pressure.Then polymerisation is carried out at 69~71 DEG C 20 hours.After the completion of polymerization, by filtering, washing, dry
To heat-expandable microsphere.Fig. 1 is the SEM pictures after heat-expandable microsphere heating expansion, and multiplication factor is 200 times, thermal expansivity
The performance of microballoon is shown in Table 2.
Embodiment 2~8：In addition to the species and consumption that change monomer, crosslinking agent, initiator and foaming agent used, other
Part is same as Example 1, and obtained different heat expansion microballoon, its performance is shown in Table 2.
Comparative example 1~3：Except change monomer used, crosslinking agent, initiator, foaming agent and polar end olefinic it is unsaturated single
The species and consumption of body, other conditions are same as Example 1, and obtained heat-expandable microsphere, its performance is shown in Table 2.
In table 1, AN：Acrylonitrile, MMA：Methyl methacrylate, MA：Methyl acrylate, ethyl acrylate；BA：Acrylic acid
Butyl ester, EMA：Metering system ethyl ester, BMA：Metering system butyl ester, TMPDMA：Trimethylol-propane trimethacrylate,
EGDMA：GDMA, DEGDE：Diethylene glycol divinyl ether, BPO：Benzoyl peroxide, AIBN：It is even
Nitrogen bis-isobutyronitrile, LPO：Lauroyl peroxide, DCPD：The cyclohexyl ester of peroxidating carbonic acid two.
The amount of the embodiment of table 1 and the different medicines used in comparative example
The performance evaluation of microballoon in the embodiment of table 2 and comparative example
1~5 can prepare Low Temperature Thermal as can be seen that being used in mixed way methyl methacrylate and methyl acrylate from table 2
Dilatancy microballoon, and methyl acrylate content increases therewith, the T of microballoonstartLower, dilatancy is better, while prepared
Microballoon has narrow particle diameter distribution.
Embodiment is compared with comparative example 1,2 it can be found that add SSS in polymerization system, can strengthened
Dispersibility of the microballoon in water, and microsphere expansion performance also significantly improves；And find SSS by contrasting
Dispersion effect is better than styrene sulfonic acid.
Specific embodiment of the invention is described above.It is to be appreciated that the invention is not limited in above-mentioned
Particular implementation, those skilled in the art can within the scope of the claims make various deformations or amendments, this not shadow
Sound substance of the invention.
Claims (10)
1. it is a kind of at low temperature with foam performance microspheres composition, by ethylenically unsaturated monomer and foaming agent group
Into, it is characterised in that the ethylenically unsaturated monomer includes the following component of percentage：
Acrylonitrile：30~90%；
Acrylic ester monomer：9.9~60%；
Monomer containing polar end 0.1~10%.
2. there is the microspheres composition of foam performance at low temperature as claimed in claim 1, it is characterised in that described
Acrylic ester monomer be methyl methacrylate and methyl acrylate in one or two.
3. there is the microspheres composition of foam performance at low temperature as claimed in claim 1, it is characterised in that described
Monomer containing polar end be styrene sulfonic acid and SSS in one or two.
4. the microspheres composition with foam performance at low temperature as claimed in claim 1, it is characterised in that by can
Microspheres weight is calculating benchmark for 100%, and the percetage by weight of foaming agent is 5~50%.
5. as described in claim 1 or 4 at low temperature with foam performance microspheres composition, it is characterised in that
The foaming agent is C4-C6Aliphatic hydrocarbon compound.
6. there is the microspheres composition of foam performance at low temperature as claimed in claim 5, it is characterised in that described
Foaming agent is C4-C5Straight chain, side chain or ring-type saturated hydrocarbons compound.
7. there is the microspheres composition of foam performance at low temperature as claimed in claim 6, it is characterised in that described
Foaming agent is selected from least one in iso-butane, isopentane, neopentane.
8. a kind of preparation method of the microspheres composition with foam performance at low temperature as claimed in claim 1,
It is characterised in that it includes following steps：After acrylonitrile, acrylic ester monomer, monomer containing polar end, iso-butane are mixed, warp
Suspension polymerisation is crossed, the microspheres composition with foam performance at low temperature is obtained.
9. preparation method as claimed in claim 7, it is characterised in that the temperature of the suspension polymerisation is 40~100 DEG C, pressure
It is 0~5.0MPa.
10. preparation method as claimed in claim 8, it is characterised in that the temperature of the suspension polymerisation is 50~85 DEG C, pressure
It is 0.2~2.0MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710042534.4A CN106832110A (en) | 2017-01-20 | 2017-01-20 | There is microspheres composition of foam performance and preparation method thereof at low temperature |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710042534.4A CN106832110A (en) | 2017-01-20 | 2017-01-20 | There is microspheres composition of foam performance and preparation method thereof at low temperature |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106832110A true CN106832110A (en) | 2017-06-13 |
Family
ID=59120904
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710042534.4A Pending CN106832110A (en) | 2017-01-20 | 2017-01-20 | There is microspheres composition of foam performance and preparation method thereof at low temperature |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106832110A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109134782A (en) * | 2018-07-17 | 2019-01-04 | 西能化工科技(上海)有限公司 | Low temperature microspheres and its preparation method and application |
| CN109749534A (en) * | 2019-01-10 | 2019-05-14 | 西能化工科技(上海)有限公司 | Automobile PVC stone-impact-proof paint and preparation method thereof |
| CN110734573A (en) * | 2018-07-18 | 2020-01-31 | 中国石油化工股份有限公司 | Production method of high-porosity PVC (polyvinyl chloride) resins |
| CN111333768A (en) * | 2018-12-18 | 2020-06-26 | 浙江海虹控股集团有限公司 | Acrylic resin thermal expansion foaming microsphere and preparation method thereof |
| CN112126007A (en) * | 2020-08-25 | 2020-12-25 | 浙江衢州巨塑化工有限公司 | Preparation method of thermal expansion polyvinylidene chloride microspheres |
| WO2022041978A1 (en) | 2020-08-25 | 2022-03-03 | 浙江衢州巨塑化工有限公司 | Thermally expandable polyvinylidene chloride microsphere and preparation method therefor |
| CN114685843A (en) * | 2020-12-29 | 2022-07-01 | 洛阳尖端技术研究院 | Thermal expansion micro-bead, pressure-sensitive adhesive containing thermal expansion micro-bead and capable of being repeatedly thermally stripped, reflective film and preparation method |
| CN115175758A (en) * | 2020-02-28 | 2022-10-11 | 松本油脂制药株式会社 | Thermally expandable microspheres, process for producing the same, and use thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102746454A (en) * | 2012-08-06 | 2012-10-24 | 长沙亦川机电设备科技有限责任公司 | Thermal expansion resin powder with high dispersity and preparation method thereof |
| CN103665419A (en) * | 2013-12-06 | 2014-03-26 | 四川达威科技股份有限公司 | Synthesis method and application method of low-medium temperature thermal expansion microspheres |
| CN104140550A (en) * | 2014-07-25 | 2014-11-12 | 扬州大学 | Fast-foaming-type thermoplastic expandable microspheres |
| CN104140549A (en) * | 2014-07-25 | 2014-11-12 | 扬州大学 | Low-temperature thermal expansion micro-sphere |
-
2017
- 2017-01-20 CN CN201710042534.4A patent/CN106832110A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102746454A (en) * | 2012-08-06 | 2012-10-24 | 长沙亦川机电设备科技有限责任公司 | Thermal expansion resin powder with high dispersity and preparation method thereof |
| CN103665419A (en) * | 2013-12-06 | 2014-03-26 | 四川达威科技股份有限公司 | Synthesis method and application method of low-medium temperature thermal expansion microspheres |
| CN104140550A (en) * | 2014-07-25 | 2014-11-12 | 扬州大学 | Fast-foaming-type thermoplastic expandable microspheres |
| CN104140549A (en) * | 2014-07-25 | 2014-11-12 | 扬州大学 | Low-temperature thermal expansion micro-sphere |
Non-Patent Citations (1)
| Title |
|---|
| 何思阳 等: "丙烯腈－丙烯酸甲酯共聚低温热膨胀微胶囊的制备与性能", 《塑料工业》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109134782B (en) * | 2018-07-17 | 2020-11-10 | 西能化工科技(上海)有限公司 | Low-temperature thermal expansion microsphere and preparation method and application thereof |
| CN109134782A (en) * | 2018-07-17 | 2019-01-04 | 西能化工科技(上海)有限公司 | Low temperature microspheres and its preparation method and application |
| CN110734573A (en) * | 2018-07-18 | 2020-01-31 | 中国石油化工股份有限公司 | Production method of high-porosity PVC (polyvinyl chloride) resins |
| CN110734573B (en) * | 2018-07-18 | 2022-06-14 | 中国石油化工股份有限公司 | Production method of high-porosity PVC resin |
| CN111333768A (en) * | 2018-12-18 | 2020-06-26 | 浙江海虹控股集团有限公司 | Acrylic resin thermal expansion foaming microsphere and preparation method thereof |
| CN111333768B (en) * | 2018-12-18 | 2022-03-29 | 浙江海虹控股集团有限公司 | Acrylic resin thermal expansion foaming microsphere and preparation method thereof |
| CN109749534A (en) * | 2019-01-10 | 2019-05-14 | 西能化工科技(上海)有限公司 | Automobile PVC stone-impact-proof paint and preparation method thereof |
| CN115175758A (en) * | 2020-02-28 | 2022-10-11 | 松本油脂制药株式会社 | Thermally expandable microspheres, process for producing the same, and use thereof |
| CN115175758B (en) * | 2020-02-28 | 2023-11-07 | 松本油脂制药株式会社 | Thermally expandable microspheres, process for production thereof, and use thereof |
| WO2022041978A1 (en) | 2020-08-25 | 2022-03-03 | 浙江衢州巨塑化工有限公司 | Thermally expandable polyvinylidene chloride microsphere and preparation method therefor |
| CN112126007A (en) * | 2020-08-25 | 2020-12-25 | 浙江衢州巨塑化工有限公司 | Preparation method of thermal expansion polyvinylidene chloride microspheres |
| CN114685843A (en) * | 2020-12-29 | 2022-07-01 | 洛阳尖端技术研究院 | Thermal expansion micro-bead, pressure-sensitive adhesive containing thermal expansion micro-bead and capable of being repeatedly thermally stripped, reflective film and preparation method |
| CN114685843B (en) * | 2020-12-29 | 2024-04-12 | 洛阳尖端技术研究院 | Thermal expansion microbead, repeatable thermal stripping pressure-sensitive adhesive containing thermal expansion microbead, reflective film and preparation method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106832110A (en) | There is microspheres composition of foam performance and preparation method thereof at low temperature | |
| CN104379647B (en) | Heat-expandable microsphere and its preparation and application | |
| CN102775545B (en) | Thermal expansibility microsphere and method for reducing residual monomers therein | |
| CN103665419B (en) | The synthetic method of middle Low Temperature Thermal expandable microspheres and application process thereof | |
| CN101341227B (en) | Heat-expandable microspheres, process for production of the same and uses thereof | |
| US4748220A (en) | Preparation of finely divided pulverulent crosslinked copolymers | |
| CN102471404B (en) | Microcapsules having polyvinyl monomers as cross-linking agents | |
| Qiu et al. | Preparation, thermal properties and thermal reliabilities of microencapsulated n-octadecane with acrylic-based polymer shells for thermal energy storage | |
| CN109456506A (en) | The heat-expandable microsphere and preparation method thereof of low residual monomer content | |
| CN108276854A (en) | Phase-change microcapsule and its preparation method and application | |
| CN104334268A (en) | Microspheres | |
| CN102775550B (en) | Medium-high temperature thermal expansibility microsphere and method for reducing residual monomers therein | |
| CN107325220A (en) | A kind of heat discoloration water-absorbent resin composition and preparation method thereof | |
| CN102906131A (en) | thickening polymer | |
| CN101010346A (en) | Method for producing polymers by dispersion polymerisation | |
| CN104558393A (en) | N-tetradecanol phase change microcapsule and preparation method thereof | |
| CN109134782B (en) | Low-temperature thermal expansion microsphere and preparation method and application thereof | |
| CN111701546A (en) | Yellowing-resistant and high temperature-resistant expandable microsphere as well as preparation method and application thereof | |
| CN110724299B (en) | Heat expansion microcapsule not easy to shrink and application thereof | |
| CN103408689A (en) | Synthetic method for instant-absorption type super absorbent resin | |
| CN102936348A (en) | Crylic acid water-absorbent resin with excellent water-retaining property and yellowing resistance and preparation method thereof | |
| CN104403049A (en) | Method for preparing phase-change microcapsule through suspension polymerization | |
| CN109847664A (en) | A kind of conduction thermal expansion type microcapsules and preparation method thereof | |
| JP5134887B2 (en) | Heat storage material | |
| CN108912383A (en) | Superhigh temperature expandable thermoplastic microspheres and its application |
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: 20170613 |