CN108084483A - Dedicated heat-swellable polymer microballoon of Corvic foaming and preparation method thereof - Google Patents
Dedicated heat-swellable polymer microballoon of Corvic foaming and preparation method thereof Download PDFInfo
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- CN108084483A CN108084483A CN201711266156.4A CN201711266156A CN108084483A CN 108084483 A CN108084483 A CN 108084483A CN 201711266156 A CN201711266156 A CN 201711266156A CN 108084483 A CN108084483 A CN 108084483A
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- 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
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- 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®
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- 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
- C08J2327/00—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 a halogen; Derivatives of such polymers
- C08J2327/02—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 a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—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 a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
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Abstract
The present invention is dedicated heat-swellable polymer microballoon of a kind of Corvic foaming and preparation method thereof, belongs to inflatable particle.By thermoplastic resin housing and it is encapsulated in the in vivo foaming agent of shell and forms, the oil phase composition that polymerisable monomer, crosslinking agent form is dispersed in Aqueous dispersions composition, in the presence of blowing agents, pass through suspension polymerization, the polymer microballoon of encapsulated blowing agent is directly made in in-stiu coating foaming agent；It is characterized in that in the oil phase composition in addition to containing polymerisable monomer, crosslinking agent, silane coupling agent is further included, the foaming agent is the mixture of isopentane, isooctane and normal octane three；Provide a kind of nucleocapsid structure is complete, particle diameter distribution uniformly, foaming agent coating efficiency it is high；And sheath polymers are heat-resist, and initial temperature during expansion is higher, highest expansion temperature is higher, expansion ratio is high, has a wider foam stabilizing Wen Cheng, and Corvic foams dedicated heat-swellable polymer microballoon.
Description
Technical field
The present invention is dedicated heat-swellable polymer microballoon of a kind of Corvic foaming and preparation method thereof.Belong to
Inflatable particle.
Background technology
Hot expandable polymer microballoon is a kind of widely used multifunctional foaming material.It is the grain with shell-core structure
The extremely small spheric granules in footpath.The kernel of microballoon is the low boiling point alkane of liquid, and the housing of microballoon is the good energy of air-tightness
Prevent the thermoplastic polyester of substance escaping in core.Under room temperature, microballoon shell is hard, and particle is small.When heated, when adding
When hot temperature is higher than the glass transition temperature of housing, case material softening inner nuclear material gasification simultaneously generates internal pressure, causes micro-
Ball expands.Volume significantly increases.Grain size before microsphere expansion is generally 5~100 μm, after expansion, and volume can be expanded as original
Tens times or even hundreds of times；After cooling, polymer shell does not bounce back, and the density of microballoon then can be from 400 original~1200kg/
m3It is reduced to 20~30kg/m3Or smaller.Moreover, when temperature is restored to and heats pervious environment temperature, the volume of microballoon
Still keep state upon inflation.That is the expansion process of microballoon is irreversible.Initial temperature when microballoon starts expansion claims
For Tstart, temperature when microsphere expansion is to maximum is known as Tmax.
Since the special structure of hot expandable polymer microballoon itself assigns the hot good foaming of expandable polymer microballoon
Performance.During for foaming of thermoplastic resin.Compared with simple gas foaming technique, have that blowing temperature is suitable, foam stabilizing area
Between it is wide in range, expansion ratio is high, cooling after do not spring back, color brilliant white, it is nontoxic odorless the features such as.Be widely used in thermoplastic resin,
The foaming processing of rubber or thermoplastic elastomer (TPE).And the better processing performance of foamed products is assigned, further improve foaming
The elasticity and resilience of product.
Corvic is one of five big general-purpose plastics, and yield is only second to polyethylene.PVC is because it is with fire-retardant, resistance to
The excellent performances such as mill, insulation, obtain extensively in fields such as light industry, agricultural, building materials, packaging, daily life, public utilities, electric power
Using.
Polyvinyl-chloride foam material is because it is with light weight, and specific strength is higher, and heat preservation and soundproof is good, good bumper and absorbing shock
Effect, thermal conductivity is low, is easy to process using mechanical means, solderable, high flame retardant, good chemical reagent resistance, and corrosion resistant is prevented
Tide, surface pigmentable, printing, overlay film, good weather resistance.
But the foaming of Corvic processing, it is necessary to operate at a higher temperature.Generally at 170~220 DEG C.
And the operating time continue it is longer.Therefore hot expandable polymer microballoon is when the foaming processing work for being applied to Corvic
When in skill, it would be desirable that hot expandable polymer microballoon starts initial temperature (Tstart during expansion with higher microballoon in itself
Value), the temperature (Tmax values) when also needed in many cases with higher microsphere expansion to maximum.
In addition, Corvic is foamed using general chemical method, expansion ratio can only achieve 20 times, be further added by just
It is very difficult.
In the prior art, the high warm expandable polymer microballoon for being suitable for Corvic foaming processing is not much
See.
Suspension polymerisation has many advantages, such as to conduct heat, and product is easily separated, impurity is less.It is widely used in polyvinyl chloride, polyphenyl second
The production of the resins such as alkene, PMMA, VDC copolymer.It is also the poly- of people's generally use that suspension polymerization, which prepares hot expended microsphere,
Conjunction method.
But in the prior art, the hot expandable polymer microballoon prepared using suspension polymerization is also existed as follows not
Foot, it is difficult to be made and be suitable for the hot expandable polymer microballoon of Corvic foaming processing：
1. particle diameter distribution is uneven.
2.. the thermoplastic resin sheath polymers poor heat resistance of hot expandable polymer microballoon, causes microspheres to exist
In resin expanded process, easy xanthochromia and rupture.
3. core-structure is imperfect, foaming agent clad ratio is low.
5. product heat resistance is not good enough.Blowing temperature is between 140~170 DEG C.
6. expansion multiplying power is low, foam stabilizing temperature journey is not wide in range enough.
7. the suspension polymerization reaction time of the prior art when 20 is small, causes product cut size to be unevenly distributed,
Foaming agent clad ratio is low.And improve production cost.
A kind of nucleocapsid structure is complete, particle diameter distribution is uniform, foaming agent coating efficiency is high；And sheath polymers heat resistance
Good, initial temperature during expansion is higher, highest expansion temperature is higher, expansion ratio is high, has wider foam stabilizing Wen Cheng, is suitable for
It is that people are expected that hot expandable polymer microballoon foaming agent is processed in Corvic foaming.
The content of the invention
It is an object of the invention to avoid above-mentioned shortcoming of the prior art, and provide a kind of suitable polyvinyl chloride tree
Fat foaming processing technology, the hot expandable polymer microballoon that expansion ratio is high, foam stabilizing temperature journey is wide in range.
The present invention also aims to provide, a kind of nucleocapsid structure is complete, particle diameter distribution is uniform, foaming agent coating efficiency
It is high；And the hot expandable polymer microballoon of the heat-resist suitable Corvic foaming processing technology of sheath polymers
Preparation method.
The purpose of the present invention can be reached by following measure：
The Corvic of the present invention foams dedicated heat-swellable polymer microballoon, by thermoplastic resin housing and by
The in vivo foaming agent composition of shell is encapsulated in, the oil phase composition that polymerisable monomer, crosslinking agent form is dispersed in Aqueous dispersions group
It closes in object, in the presence of blowing agents, by suspension polymerization, the poly- of encapsulated blowing agent is directly made in in-stiu coating foaming agent
Close object microballoon；It is characterized in that：
1. the polymerisable monomer in oil phase composition described in is by acrylonitrile, methacrylonitrile, methyl methacrylate, first
Base butyl acrylate, styrene, 1,1- dichloroethylene, methacrylic acid and acrylic acid composition；
2. in oil phase composition described in addition to containing polymerisable monomer, crosslinking agent, silane coupling agent group is further included
Point；
3. foaming agent described in is the mixture of isopentane, isooctane and normal octane three；
4. Aqueous dispersions composition described in includes scattered being helped by what deionized water, sodium chloride, Ludox and dispersant formed
Agent component and the dispersion stabilizer component being formulated by absolute ethyl alcohol, hydrazine hydrate and sodium citrate；
5. the pH of Aqueous dispersions composition system described in is controlled between 2.9~3.1；
The dedicated heat-swellable polymer microballoon of the Corvic foaming reaches following technical indicator：
The excellent expansion character of the dedicated heat-swellable polymer microballoon of Corvic foaming of the present invention, relies on
In sheath polymers foot is provided for microballoon for the good barrier property that kernel foaming agent provides with rational foaming agent is formulated
Pressure in enough expansions.Since pressure caused by kernel and shell thermoplasticity compatibility are proper, so that the microballoon exhibition of the present invention
Reveal good expansion character, achieve preferable technique effect.
First, the polymerisable monomer in oil phase composition is by acrylonitrile, methacrylonitrile, methyl methacrylate, methyl
Butyl acrylate, styrene, 1,1- dichloroethylene, methacrylic acid and acrylic acid composition；
Acrylonitrile monemer has good heat resistance and crystal property；Hydrogen bond in acrylonitrile molecular structure to polymerize
Obtained film layer transmission coefficient is small；The copolymer that 1,1- dichloroethylene in formula participates in has relatively low permeability, Neng Goufu
The good air-tightness of housing polymer is given, therefore, the polymer that the two is formed has excellent barrier property and air-tightness；
Methacrylonitrile, methyl methacrylate, butyl methacrylate can improve the thermoplasticity of copolymer；Styrene energy
Enough improve the heat resistance of microballoon and pressure-resistant slight；
Methacrylic acid and acrylic acid have high crystallinity and high glass transition temperature, participate in copolymerization energy
Enough improve the softening temperature of polymer.Although good to make up acrylonitrile component heat resistance, high temperature elastomeric is poor not
Foot.
Methacrylonitrile, methyl methacrylate, butyl methacrylate play control rate of polymerization, have control polymerization
The elastic stretch rate of object and softening point temperature improve the function of the toughness of polymeric shells.
Addition crosslinking agent can increase the strength of materials of the sheath polymers in elastomeric state and viscous state, improve microsphere expansion
And heat resistance.In the oil phase composition of the present invention in addition to containing polymerisable monomer, crosslinking agent, silane coupling agent group is further included
Point；Crosslinking agent and coupling agent have linear copolymerization point, and crosslinking and coupling reaction by polymer can further expand copolymerization
The elastic range of object, and its heat-resistant stability is improved, it is made that important technical contribution for the completing the present invention of the task.
The foaming agent that the present invention uses is the mixture of isopentane, isooctane and normal octane three, the boiling point of foaming agent and
Preferred compositing range, it is suitable to be provided for the dedicated heat-swellable polymer microballoon of Corvic foaming of the invention
Expansion temperature and the bulbs of pressure.For preparing technical contribution is made that with good expansion character and larger expansion ratio.
Aqueous dispersions composition of the present invention includes point being made of deionized water, sodium chloride, Ludox and dispersant
Dissipate adjuvant component and the dispersion stabilizer component being formulated by absolute ethyl alcohol, hydrazine hydrate and sodium citrate；It is the skill of the present invention
Important component in art scheme.The present inventor in experiments it is found that, Aqueous dispersions auxiliary agent using the present invention
Microsphere particle prepared by composition is under the microscope in the preferable spheroidal of homogeneity, using by absolute ethyl alcohol, hydrazine hydrate and lemon
The dispersion stabilizer that lemon acid sodium is formulated after the completion of monomer reaction, easily filters and convenient for separation, and microsphere particle is more preferable, and
And the reaction time can be shortened, by original 20 it is small when shorten to 10~12 it is small when.
The pH of the Aqueous dispersions composition system is controlled between 2.9~3.1；It is preferred technical solution.
The purpose of the present invention can also be reached by following measure：
The dedicated heat-swellable polymer microballoon of Corvic foaming of the present invention, the polymerisable monomer is by such as
Under according to mass percentage raw material form：
The crosslinking agent addition is the 0.1%~0.5% of above-mentioned polymerized monomer gross mass；
The silane coupling agent addition is the 2%~5% of above-mentioned polymerized monomer gross mass.
It is preferred technical solution.
The dedicated heat-swellable polymer microballoon of Corvic foaming of the present invention, the polymerisable monomer is by such as
Under according to mass percentage raw material form：
The crosslinking agent addition is the 0.2%~0.4% of above-mentioned polymerized monomer gross mass；
The silane coupling agent addition is the 3%~4% of above-mentioned polymerized monomer gross mass.
It is further preferred technical solution.
The dedicated heat-swellable polymer microballoon of Corvic foaming of the present invention, the polymerisable monomer is by such as
Under according to mass percentage raw material form：
The crosslinking agent addition is the 0.3% of above-mentioned polymerized monomer gross mass；
The silane coupling agent addition is the 3.7% of above-mentioned polymerized monomer gross mass.
It is a preferred technical solution.
The Corvic of the present invention foams dedicated heat-swellable polymer microballoon, in the oil phase composition
Silane coupling agent is KH550, KH560, KH570, KH792, DL602, a kind of in DL171.
The dedicated heat-swellable polymer microballoon of Corvic foaming of the present invention, the crosslinking agent is dimethyl
Acrylic acid glycol ester (EGDMA), trimethylol-propane trimethacrylate (TMPTMA), polyethylene glycol 400 dimethyl propylene
One kind in olefin(e) acid ester (PEG400DMA), 1,6 hexanediol dimethacrylates (HDDMA).
The dedicated heat-swellable polymer microballoon of Corvic foaming of the present invention, the suspension polymerization are adopted
Initiator is dicetyl peroxydicarbonate two-(2- ethylhexyls), 2, the group of one kind or the two in 2 '-azodiisobutyronitrile
Close object.
The Corvic of the present invention foams dedicated heat-swellable polymer microballoon, the foaming agent by as follows according to
The raw material composition of mass percentage：
Isopentane 75~90
Isooctane 5~25
Normal octane 5~25.
It is preferred compositing range.
The dedicated heat-swellable polymer microballoon of Corvic foaming of the present invention, the foaming agent addition is poly-
Close the 12%~35% of monomer gross mass.It is preferred technical solution.
The dedicated heat-swellable polymer microballoon of Corvic foaming of invention, the foaming agent addition is polymerization
The 20%~30% of monomer gross mass.It is most preferred technical solution.
The dedicated heat-swellable polymer microballoon of Corvic foaming of the present invention, the Aqueous dispersions composition
Dispersing aid component according to the raw material of mass fraction meter by forming as follows
The dedicated heat-swellable polymer microballoon of Corvic foaming of the present invention, the dispersant is polyethylene pyrrole
Pyrrolidone or polyvinyl alcohol are preferred technical solutions.
The dedicated heat-swellable polymer microballoon of Corvic foaming of the present invention, the Aqueous dispersions composition
Dispersion stabilizer according to the raw material of mass fraction meter by forming as follows：
Absolute ethyl alcohol 1.7~20
The hydrazine hydrate aqueous solution 1.7~20 of 1wt%
The aqueous citric acid solution 1.7~20 of 1wt%.
It is preferred technical solution.
The preparation method of the dedicated heat-swellable polymer microballoon of Corvic foaming of the present invention, it is characterised in that
The dispersion stabilizer of the Aqueous dispersions composition according to the raw material of mass fraction meter by forming as follows：
Absolute ethyl alcohol 1.7~20
The hydrazine hydrate aqueous solution 1.7~20 of 1wt%
The aqueous citric acid solution 1.7~20 of 1wt%.
The preparation method of the dedicated heat-swellable polymer microballoon of Corvic foaming of the present invention, it is characterised in that
Include the following steps：
The preparation of one, Aqueous dispersions compositions
1. the preparation of aqueous solution of raw material
A. the preparation of dispersant solution
In the deionized water of 160 parts by weight, 0.12~1 parts by weight of dispersant are added in, dissolves, stir evenly, it is spare；
B. the preparation of water phase inhibitor solution
The sodium chloride of 36~120 parts by weight is added in 350 parts by weight of deionized water, dissolving is spare；
C.. the preparation of dispersing aid sodium nitrite in aqueous solution
The sodium nitrite in aqueous solution of 1wt% is prepared with deionized water, it is spare；
D. the preparation of hydrazine hydrate aqueous solution
The hydrazine hydrate aqueous solution of 1wt% is prepared with deionized water, it is spare；
E. the preparation of aqueous citric acid solution
The aqueous citric acid solution solution of 1wt% is prepared with deionized water, it is spare；
2. the preparation of dispersing aid components
In mixing and stirring tank, by the dispersant solution of a preparations, the b water phase inhibitor solutions prepared and c preparations
1wt% 1.70~10 parts by weight of sodium nitrite in aqueous solution, be sufficiently mixed uniformly after, under stirring, be slowly added dropwise commercially available
8~32 parts by weight of 20wt% silicon sol solutions, it is stirred 15 minutes, dispersing aid component is made, it is spare；
3. the preparation of dispersion stabilizer components
By 1.7~20 parts by weight of absolute ethyl alcohol, 1.7~20 weight of hydrazine hydrate aqueous solution of the 1wt% of above-mentioned d preparation
Part, 1.7~20 parts by weight of aqueous citric acid solution of the e 1wt% prepared are stirred, and dispersion stabilizer component is made, standby
With；
4. the preparation of Aqueous dispersions compositions
In the step 1 Aqueous dispersions assistant composition that 2. prepared by item, the step dispersion stabilizer group that 3. item is prepared is added in
Point, it is sufficiently stirred, mixing is uniformly dispersed, and Aqueous dispersions composition is made, spare；
The preparation of two, oil phase compositions
By 25~74 parts by weight of acrylonitrile, 2~15 parts by weight of methacrylonitrile, 5~40 parts by weight of methyl methacrylate,
2~8 parts by weight of butyl methacrylate, 2~15 parts by weight of styrene, 3~30 parts by weight of 1,1- dichloroethylene, methacrylic acid
5~30 parts by weight, acrylic acid 2~10 weight point, the mixing of 0.1~0.5 parts by weight of crosslinking agent, 2~5 parts by weight of silane coupling agent,
Form the housing raw material components of the dedicated heat-swellable polymer microballoon of the Corvic foaming；Order adds in successively again
9.0~31.5 parts by weight of isopentane, 0.6~8.75 parts by weight of isooctane；0.6~8.75 parts by weight of normal octane；Initiator 0.1~
2.0 parts of parts by weight, mixing, dissolving, are made Unctuous compositions；
Three, mixing, homogenous disperse
In oil phase composition input homogeneous mixer prepared by Aqueous dispersions composition and step 2 prepared by step 1,
Under 2000~10000 revs/min of rotating speed, homogenous disperse to the oil phase drop diameter control being scattered in water phase is 5~50
Between micron；
Four, polymerize
The suspension of step 3 homogenous disperse qualification is put into polymeric kettle, nitrogen displacement, and 0.15~2MPa of pressurize, delay
Slowly it is warming up to 45 DEG C~75 DEG C to start to react, under at the uniform velocity stirring, when reaction 10~12 is small；
Five, filterings, washing, drying
Step 4 polymerizate filters, and filter cake is washed with deionized, and oven drying pulverizes and sieves, and polyvinyl chloride is made
Resin expanded dedicated heat-swellable polymer microballoon.
The application of the dedicated heat-swellable polymer microballoon of Corvic foaming of the present invention, it is characterised in that be used for
Using Corvic and polystyrene resin, polyvinyl resin, acrylic resin, thermoplastic polyurethane and phenolic resin as
Raw material produces the foaming agent of its expanded material.
Dedicated heat-swellable polymer microballoon of Corvic foaming of the present invention and preparation method thereof, compared to existing
Technology can generate following good effect：
1. providing, a kind of nucleocapsid structure is complete, particle diameter distribution is uniform, foaming agent coating efficiency is high；And shell polymerize
Object is heat-resist, and initial temperature during expansion is higher, highest expansion temperature is higher, expansion ratio is high, has wider foam stabilizing temperature
Journey, the Corvic foaming for being suitable for thermoplastic resin, rubber or the application of thermoplastic elastomer foaming processing technology are special
Heat-swellable polymer microballoon.
2. providing, a kind of nucleocapsid structure is complete, particle diameter distribution is uniform, foaming agent coating efficiency is high；And shell polymerize
Object is heat-resist, and initial temperature during expansion is higher, highest expansion temperature is higher, expansion ratio is high, has wider foam stabilizing temperature
Journey, the Corvic foaming for being suitable for thermoplastic resin, rubber or the application of thermoplastic elastomer foaming processing technology are special
The preparation method of heat-swellable polymer microballoon.
3. solves the technical issues of heat-swellable polymer microballoon product cut size is unevenly distributed.Polyvinyl chloride obtained
Resin expanded dedicated heat-swellable polymer microballoon average grain diameter is between 5~60 μm.Preferred scheme reaches 5~15 μm.
4. improve the thermoplastic resin sheath polymers heat resistance initial expansion temperatures of hot expandable polymer microballoon
135~190 DEG C, 220~245 DEG C of highest expansion temperature.
5. solve thermo-expandable microspheres in resin expanded process, the technical issues of easy xanthochromia and rupture.220
DEG C do not turn yellow the time >=15 minutes；220 DEG C of not rupture time >=20 minute.Product whiteness % >=90%.
6. microballoon core-structural integrity, bag rate reaches >=95% in foaming agent.
Reach 7. expansion multiplying power increases substantially between 90~120.
8.. the suspension polymerization time from original 20 it is small when foreshorten to 10~12 it is small when.Reduce production cost.
Specific embodiment
The present invention will now be further detailed embodiment：
Embodiment 1~12
The dedicated heat-swellable polymer microballoon of Corvic foaming of the present invention is prepared in accordance with the following steps
The preparation of one, Aqueous dispersions compositions
1. the preparation of aqueous solution of raw material
A. the preparation of dispersant solution
In the deionized water of 160 parts by weight, 0.12~1 parts by weight of dispersant are added in, dissolves, stir evenly, it is spare；
B. the preparation of water phase inhibitor solution
The sodium chloride of 36~120 parts by weight is added in 350 parts by weight of deionized water, dissolving is spare；
C.. the preparation of dispersing aid sodium nitrite in aqueous solution
The sodium nitrite in aqueous solution of 1wt% is prepared with deionized water, it is spare；
D. the preparation of hydrazine hydrate aqueous solution
The hydrazine hydrate aqueous solution of 1wt% is prepared with deionized water, it is spare；
E. the preparation of aqueous citric acid solution
The aqueous citric acid solution solution of 1wt% is prepared with deionized water, it is spare；
2. the preparation of dispersing aid components
In mixing and stirring tank, by the dispersant solution of above-mentioned a preparation, the b water phase inhibitor solutions prepared and c
1.70~10 parts by weight of sodium nitrite in aqueous solution of the 1wt% of preparation after being sufficiently mixed uniformly, under stirring, are slowly added dropwise commercially available
8~32 parts by weight of 20wt% silicon sol solutions, it is stirred 15 minutes, dispersing aid component is made, it is spare；
3. the preparation of dispersion stabilizer components
By 1.7~20 parts by weight of absolute ethyl alcohol, 1.7~20 weight of hydrazine hydrate aqueous solution of the 1wt% of above-mentioned d preparation
Part, 1.7~20 parts by weight of aqueous citric acid solution of the e 1wt% prepared are stirred, and dispersion stabilizer component is made, standby
With；
4. the preparation of Aqueous dispersions compositions
In the step 1 Aqueous dispersions assistant composition that 2. prepared by item, the step dispersion stabilizer group that 3. item is prepared is added in
Point, it is sufficiently stirred, mixing is uniformly dispersed, and Aqueous dispersions composition is made, spare；
The preparation of two, oil phase compositions
By 25~74 parts by weight of acrylonitrile, 2~15 parts by weight of methacrylonitrile, 5~40 parts by weight of methyl methacrylate,
2~8 parts by weight of butyl methacrylate, 2~15 parts by weight of styrene, 3~30 parts by weight of 1,1- dichloroethylene, methacrylic acid
5~30 parts by weight, acrylic acid 2~10 weight point, the mixing of 0.1~0.5 parts by weight of crosslinking agent, 2~5 parts by weight of silane coupling agent,
Form the housing raw material components of the dedicated heat-swellable polymer microballoon of the Corvic foaming；Order adds in successively again
9.0~31.5 parts by weight of isopentane, 0.6~8.75 parts by weight of isooctane；0.6~8.75 parts by weight of normal octane；Initiator 0.1~
2.0 parts of parts by weight, mixing, dissolving, are made Unctuous compositions；
Three, mixing, homogenous disperse
In oil phase composition input homogeneous mixer prepared by Aqueous dispersions composition and step 2 prepared by step 1,
Under 2000~10000 revs/min of rotating speed, homogenous disperse to the oil phase drop diameter control being scattered in water phase is 5~50
Between micron；
Four, polymerize
The suspension of step 3 homogenous disperse qualification is put into polymeric kettle, nitrogen displacement, and 0.15~2MPa of pressurize, delay
Slowly it is warming up to 45 DEG C~75 DEG C to start to react, under at the uniform velocity stirring, when reaction 10~12 is small；
Five, filterings, washing, drying
Step 4 polymerizate filters, and filter cake is washed with deionized, and oven drying pulverizes and sieves, and polyvinyl chloride is made
Resin expanded dedicated heat-swellable polymer microballoon.
Embodiment 1~12 is listed in table 1, polyvinyl chloride prepared by embodiment 1~12 according to the raw material proportioning of mass fraction meter
Resin expanded dedicated heat-swellable polymer microballoon technical indicator is listed in table 2
1 embodiment 1~12 of table according to mass fraction meter raw material proportioning
The dedicated heat-swellable polymer microballoon technical indicator of Corvic foaming prepared by 2 embodiment 1~12 of table
Explanations of one, on foaming agent conservation rate：
1. definition：In the present invention, by heat expand at the temperature at which foaming agent interior bag rate compared be enclosed in heating
The percentage of the interior bag rate of the foaming agent in heat-expandable microsphere before expansion is defined as the foaming agent conservation rate under test temperature.
2. test method：Heat-expandable microsphere Wr (g) is added in the aluminum disk of outer diameter 5.2mm, with the liter of 10 DEG C/min
Warm speed is heated to 80 DEG C from 20 DEG C, in order to remove moisture contained in heat-expandable microsphere, 30min is kept at 80 DEG C and is confirmed
Weight change is constant.300 DEG C are heated to from 80 DEG C with 10 DEG C/min of heating rate, measures the weight Ws (g) under Tav (DEG C).Profit
With the amount CR3 (weight %) for the foaming agent that following calculating formulas (G) calculating is released from heat-expandable microsphere, following calculating formulas are utilized
(H) foaming agent conservation rate Rb (%) is calculated.
According to Rb (%) according to following foaming agent conservation rate when judging that benchmark evaluation heating expands.The instrument used is
Show that poor type shows differential thermal Libra.
((Wr-Ws)/Wr × 100)-CW=CR3 (G)
Rb=(CR2-CR3)/CR2 (H)
Two, microballoon expansion ratio assay methods
It is crushed after product drying, surveys apparent density first, then the microspheres of 0.5g are filled into the test tube of 50ml
In, tiling is uniform, is put into baking oven, and then with the heating rate of 10 DEG C/min, sample is added in the range of 20 to 200 DEG C
Heat, when observing that microsphere volume starts variation for start DEG C of initial expansion temperature, when expanding noodles reach maximum swelling scale
Temperature for maximum swelling temperature, and volume during according to the apparent density, quality, maximum swelling of starting calculates expansion multiplying power.
Claims (15)
- The dedicated heat-swellable polymer microballoon 1. a kind of Corvic foams, by thermoplastic resin housing and is encapsulated in The in vivo foaming agent composition of shell, the oil phase composition that polymerisable monomer, crosslinking agent form is dispersed in Aqueous dispersions composition, In the presence of blowing agents, by suspension polymerization, in-stiu coating foaming agent, the polymer that encapsulated blowing agent is directly made is micro- Ball；It is characterized in that：1. the polymerisable monomer in oil phase composition described in is by acrylonitrile, methacrylonitrile, methyl methacrylate, methyl-prop Olefin(e) acid butyl ester, styrene, 1,1- dichloroethylene, methacrylic acid and acrylic acid composition；2. in oil phase composition described in addition to containing polymerisable monomer, crosslinking agent, silane coupling agent component is further included；3. foaming agent described in is the mixture of isopentane, isooctane and normal octane three；4. Aqueous dispersions composition described in includes the dispersing aid group being made of deionized water, sodium chloride, Ludox and dispersant The dispersion stabilizer component divided and be formulated by absolute ethyl alcohol, hydrazine hydrate and sodium citrate；5. the pH of Aqueous dispersions composition system described in is controlled between 2.9~3.1；The dedicated heat-swellable polymer microballoon of the Corvic foaming reaches following technical indicator：
- The dedicated heat-swellable polymer microballoon 2. the Corvic according to claim 1 foams, it is characterised in that described Polymerisable monomer be made of the raw material as follows according to mass percentage：The crosslinking agent addition is the 0.1%~0.5% of above-mentioned polymerized monomer gross mass；The silane coupling agent addition is the 2%~5% of above-mentioned polymerized monomer gross mass.
- The dedicated heat-swellable polymer microballoon 3. the Corvic according to claim 1 foams, it is characterised in that described Polymerisable monomer be made of the raw material as follows according to mass percentage：The crosslinking agent addition is the 0.2%~0.4% of above-mentioned polymerized monomer gross mass；The silane coupling agent addition is the 3%~4% of above-mentioned polymerized monomer gross mass.
- The dedicated heat-swellable polymer microballoon 4. the Corvic according to claim 1 foams, it is characterised in that described Polymerisable monomer be made of the raw material as follows according to mass percentage：The crosslinking agent addition is the 0.3% of above-mentioned polymerized monomer gross mass；The silane coupling agent addition is the 3.7% of above-mentioned polymerized monomer gross mass.
- The dedicated heat-swellable polymer microballoon 5. the Corvic according to claim 1 foams, it is characterised in that described Oil phase composition in silane coupling agent be KH550, KH560, KH570, KH792, DL602 are a kind of in DL171.
- The dedicated heat-swellable polymer microballoon 6. the Corvic according to claim 1 foams, it is characterised in that raw material Crosslinking agent described in component is ethylene glycol dimethacrylate (EGDMA), trimethylol-propane trimethacrylate (TMPTMA), polyethylene glycol 400 dimethylacrylate (PEG400DMA), 1,6 hexanediol dimethacrylates (HDDMA) In one kind.
- The dedicated heat-swellable polymer microballoon 7. the Corvic according to claim 1 foams, it is characterised in that described The initiator that uses of suspension polymerization be dicetyl peroxydicarbonate two-(2- ethylhexyls), 2, in 2 '-azodiisobutyronitrile One kind or combination object.
- The dedicated heat-swellable polymer microballoon 8. the Corvic according to claim 1 foams, it is characterised in that described Foaming agent is made of the raw material as follows according to mass percentage：Isopentane 75~90Isooctane 5~25Normal octane 5~25.
- 9. it foams dedicated heat-swellable polymer microballoon according to the Corvic of claim 1 and claim 8, It is characterized in that 12%~35% that the foaming agent addition is polymerized monomer gross mass.
- 10. it foams dedicated heat-swellable polymer microballoon according to the Corvic of claim 1 and claim 8, It is characterized in that the foaming agent addition is the 20%~30% of polymerized monomer gross mass.
- The dedicated heat-swellable polymer microballoon 11. the Corvic according to claim 1 foams, it is characterised in that described The dispersing aid component of Aqueous dispersions composition according to the raw material of mass fraction meter by forming as follows：
- The dedicated heat-swellable polymer microballoon 12. the Corvic according to claim 9 foams, it is characterised in that described Dispersant is polyvinylpyrrolidone or polyvinyl alcohol.
- The dedicated heat-swellable polymer microballoon 13. the Corvic according to claim 1 foams, it is characterised in that described The dispersion stabilizer of Aqueous dispersions composition according to the raw material of mass fraction meter by forming as follows：Absolute ethyl alcohol 1.7~20The hydrazine hydrate aqueous solution 1.7~20 of 1wt%The aqueous citric acid solution 1.7~20 of 1wt%.
- The preparation method of dedicated heat-swellable polymer microballoon 14. a kind of Corvic of claim 1 foams, it is special Sign is to include the following steps：The preparation of one, Aqueous dispersions compositions1. the preparation of aqueous solution of raw materialA. the preparation of dispersant solutionIn the deionized water of 160 parts by weight, 0.12~1 parts by weight of dispersant are added in, dissolves, stir evenly, it is spare；B. the preparation of water phase inhibitor solutionThe sodium chloride of 36~120 parts by weight is added in 350 parts by weight of deionized water, dissolving is spare；C.. the preparation of dispersing aid sodium nitrite in aqueous solutionThe sodium nitrite in aqueous solution of 1wt% is prepared with deionized water, it is spare；D. the preparation of hydrazine hydrate aqueous solutionThe hydrazine hydrate aqueous solution of 1wt% is prepared with deionized water, it is spare；E. the preparation of aqueous citric acid solutionThe aqueous citric acid solution solution of 1wt% is prepared with deionized water, it is spare；2. the preparation of dispersing aid componentsIn mixing and stirring tank, by the dispersant solution of above-mentioned a preparation, the b water phase inhibitor solutions prepared and c preparations 1wt% 1.70~10 parts by weight of sodium nitrite in aqueous solution, after being sufficiently mixed uniformly, under stirring, the 20wt% that is slowly added dropwise 8~32 parts by weight of silicon sol solution, it is stirred 15 minutes, dispersing aid component is made, it is spare；3. the preparation of dispersion stabilizer componentsBy 1.7~20 parts by weight of absolute ethyl alcohol, it is above-mentioned d preparation 1wt% 1.7~20 parts by weight of hydrazine hydrate aqueous solution, e 1.7~20 parts by weight of aqueous citric acid solution of the 1wt% of preparation are stirred, and dispersion stabilizer component is made, spare；4. the preparation of Aqueous dispersions compositionsIn the step 1 Aqueous dispersions assistant composition that 2. prepared by item, the step dispersion stabilizer component that 3. item is prepared is added in, It is sufficiently stirred, mixing is uniformly dispersed, and Aqueous dispersions composition is made, spare；The preparation of two, oil phase compositionsBy 25~74 parts by weight of acrylonitrile, 2~15 parts by weight of methacrylonitrile, 5~40 parts by weight of methyl methacrylate, methyl 2~8 parts by weight of butyl acrylate, 2~15 parts by weight of styrene, 3~30 parts by weight of 1,1- dichloroethylene, methacrylic acid 5~ 30 parts by weight, acrylic acid 2~10 weight point, the mixing of 0.1~0.5 parts by weight of crosslinking agent, 2~5 parts by weight of silane coupling agent, composition The housing raw material components of the dedicated heat-swellable polymer microballoon of the Corvic foaming；Order adds in isoamyl successively again 9.0~31.5 parts by weight of alkane, 0.6~8.75 parts by weight of isooctane；0.6~8.75 parts by weight of normal octane；Initiator 0.1~2.0 Part parts by weight, mixing, dissolving, are made Unctuous compositions；Three, mixing, homogenous disperseIn oil phase composition input homogeneous mixer prepared by Aqueous dispersions composition and step 2 prepared by step 1, Under 2000~10000 revs/min of rotating speed, homogenous disperse is micro- 5~50 to the oil phase drop diameter control being scattered in water phase Between rice；Four, polymerizeThe suspension of step 3 homogenous disperse qualification is put into polymeric kettle, nitrogen displacement, and 0.15~2MPa of pressurize, slowly rise Temperature starts to react to 45 DEG C~75 DEG C, under at the uniform velocity stirring, when reaction 10~12 is small；Five, filterings, washing, dryingStep 4 polymerizate filters, and filter cake is washed with deionized, and oven drying pulverizes and sieves, and Corvic is made Foam dedicated heat-swellable polymer microballoon.
- The application of dedicated heat-swellable polymer microballoon 15. the Corvic of claim 1 foams, it is characterised in that use In with Corvic and polystyrene resin, polyvinyl resin, acrylic resin, thermoplastic polyurethane and phenolic resin The foaming agent of its expanded material is produced for raw material.
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