CN106317445A - Supported crystalline hydrate foaming agent, and preparation method and applications thereof - Google Patents
Supported crystalline hydrate foaming agent, and preparation method and applications thereof Download PDFInfo
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- CN106317445A CN106317445A CN201510369742.6A CN201510369742A CN106317445A CN 106317445 A CN106317445 A CN 106317445A CN 201510369742 A CN201510369742 A CN 201510369742A CN 106317445 A CN106317445 A CN 106317445A
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Abstract
The invention discloses a supported crystalline hydrate foaming agent, and a preparation method and applications thereof. The foaming agent comprises a carrier and salt hydrate crystals supported on the surface of the carrier. The preparation method comprises the following steps: dissolving crystalline salts or hydrates of crystalline salts into water, adding a carrier, evenly stirring, keeping on stirring, heating to evaporate water to obtain a slurry-like product, drying, grinding, and sieving to obtain the supported crystalline hydrate foaming agent. The foaming agent is used as an additive and is applied to the preparation of a polymer foamed material. The application method comprises the following steps: mixing the foaming agent with polymers and optical aids to obtain a composition, heating, and carrying out moulding processing. Water is taken as the foaming component of the provided supported crystalline hydrate foaming agent. The supported crystalline hydrate foaming agent can be used as an additive and is directly mixed with polymers; after mixing, the mixture is subjected to a heat treatment and moulding to obtain a polymer foamed material; the foaming agent has a repeated foaming performance, the preparation and application process is safe and environment-friendly, the cost is low, and the preparation method is suitable for massive industrial production.
Description
Technical field
The present invention relates to the foaming agent for preparing polymer foams, be specifically related to
A kind of supported crystalline hydrate foaming agent, its preparation method and application.
Background technology
Polymer foams has the multiple Optimalities such as light weight, heat-insulating sound-insulating, vibration damping
Can, apply quite varied.The preparation of polymer foams, be unable to do without foaming agent
Use.
Foaming agent is broadly divided into physical blowing agent and CBA.Wherein, chemistry is sent out
Infusion utilizes chemical reaction to produce gas and foams, such as inorganic carbonate and carbon
Acid hydrogen salt or organically azo-compound, this type of foaming agent mostly need to be at special chemistry
Could apply under reaction condition, narrow application range, due to chemical reaction poor controllability,
The homogeneity using its polymer foams prepared is poor, and application process is dangerous
High；Physical blowing agent is gasified by foaming component and completes foaming process, typical thing
Haircut infusion includes chloro-fluoro-carbon kind, hydrogen fluorohydrocarbon class, alkanes, supercritical carbon dioxide
Deng, described hydro carbons physical blowing agent all has environmental hazard and security risk, and too much
CO2 emission can increase greenhouse effect, is unfavorable for sustainable development, and preparation is super
The energy consumption of critical carbon dioxide and cost are high, are unsuitable for large-scale production.
From the standpoint of multiple, the physical blowing agent with water as foaming component has tradition
The advantage that foaming agent is incomparable.CN201210157693.6 discloses a kind of water and sends out
The preparation method of foamed polystyrene, the method is when preparing expanding styrene polymer granules
Employ water-absorbing resin sodium polyacrylate Nano microsphere, it is thus achieved that be coated with aqueous Nanometer core
Polystyrene microsphere, the water vapor in heated Nanometer core realizes foamed polystyrene
Process.The method will contain water particle based on dispersion copolymerization method when preparing polymer microballoon
Being coated on inside polymer spheres, for its embodiment, the method is not suitable for
Water is added polymer as additive component by Polymer Processing formative stage to be implemented to send out
Bubble.CN201310606455.3 discloses a kind of polylactic acid with water as foaming component bubble
Foam, contains isocyanate compound and azodicarbonamide in the formula announced,
Therefore the expanded polylactic acid process of this report is the most merely the contribution of water, water and isocyanide
Produced by the carbon dioxide of acid esters reaction generation and azodicarbonamide decomposes
Nitrogen has also assisted in the forming process of polylactic acid foam.
In sum, there is no a kind of with water as foaming component so far, can be as additive
Directly and carry out thermo forming after polymer mixed and obtain polymer foams, tool
There is a repetition foaming capacity, and preparation and the safe and environment-friendly foaming agent of application process.
Summary of the invention
In order to overcome the problems referred to above, the present inventor is to being used for preparing polymer foams
Foaming agent carried out studying with keen determination, found that: use the ad hoc approach will suitably
Salt hydrate crystal load is in suitable carrier surface, and regulates the two usage ratio,
A kind of novel load crystalline hydrate for preparing polymer foams can be prepared
Foaming agent, described foaming agent, can be as additive directly with poly-with water as foaming component
Carry out thermo forming after compound mixing and obtain polymer foams, have and repeat to send out
Bubble ability, and preparation and application process safe and environment-friendly, low cost, be suitable to extensive
Commercial production.
It is an object of the invention to provide following aspect:
(1) a kind of supported crystalline hydrate foaming agent, this foaming agent includes: carrier
With the salt hydrate crystal being carried on carrier surface.
(2) a kind of supported crystalline hydrate foaming agent as described in above-mentioned (1)
Preparation method, the method includes:
Step 1), by soluble in water for the hydrate of crystalline salt or crystalline salt, add
Carrier, stirring, obtain uniform dispersion liquid；
Step 2), be kept stirring for, to step 1) heating of the dispersion liquid that obtains, make moisture
Volatilization, obtains paste-like product；
Step 3), by step 2) the paste-like product heats that obtains dries, size-reduced,
Sieve, obtain described supported crystalline hydrate foaming agent.
(3) a kind of supported crystalline hydrate foaming agent as described in above-mentioned (1)
Application, it is characterised in that should as additive using supported crystalline hydrate foaming agent
Preparation for polymer foams.
(4) a kind of supported crystalline hydrate foaming agent as described in above-mentioned (3)
Application process, the method includes:
Step 1), by supported crystalline hydrate foaming agent, polymer and optional helping
Agent mixes, and obtains compositions；
Step 2), by step 1) heating of the compositions that obtains, and carry out processing and forming.
The present invention is had the advantage that to include:
(1) the supported crystalline hydrate foaming agent that the present invention provides belongs to water for sending out
The physical blowing agent of bubble component, during using it to prepare polymer foams
Will not produce poisonous, harmful gas, environmentally friendly, meanwhile, the noninflammability of water makes
The preparation process obtaining polymer foams is safer；
(2) the dehydration temperature tool of the supported crystalline hydrate foaming agent that the present invention provides
There is adjustability, can be regulated by the load capacity of regulation carrier surface salt hydrate crystal
The dehydration temperature of foaming agent so that the dehydration of described supported crystalline hydrate foaming agent
In the range of temperature is in polymer hot processing temperature, to meet multiple polymers foam material
The preparation demand of material, applied range；
(3) the supported crystalline hydrate foaming agent that the present invention provides is by inorganic carrier
Form with salt hydrate crystal, nontoxic, environmentally friendly, and storing process peace
Loopful is protected；
(4) the preparation method letter of the supported crystalline hydrate foaming agent that the present invention provides
Single, it is easy to operation, safe preparation process is high, controllability is strong, and raw material is easy to get,
Low price, is suitable to large-scale industrial production；
(5) the supported crystalline hydrate foaming agent that the present invention provides can be as additive
With polymer mixed, for the preparation of polymer foams, use simple, it is easy to
Realize, and universality is strong, can be used for multiple with solid-state or the thermoplasticity of liquid and thermosetting
Property polymer is that polymer foams prepared by raw material；
(6) present invention provide supported crystalline hydrate foaming agent have repeat foaming
Ability, uses its polymer foams prepared can continue when carrying out reworking
Recycling of foaming, beneficially polymer foams；
(7) the application process letter of the supported crystalline hydrate foaming agent that the present invention provides
Easy row, can complete, heating-up temperature during polymer routine thermo forming
Low, energy consumption is low, and applied range is suitable to commercial production.
Detailed description of the invention
Below by experimental example and embodiment, the present invention is described in more detail.Pass through
These explanations, the features and advantages of the invention will become more apparent from clearly.
According to the first aspect of the invention, it is provided that a kind of supported crystalline hydrate foams
Agent, this foaming agent includes carrier and is carried on the salt hydrate crystal of carrier surface, excellent
Selection of land, described salt hydrate crystal forms salt through physical deposition on the surface of carrier and is hydrated
Thing crystal layer.
Described salt hydrate crystal is the component playing foaming effect in foaming agent, tool
Body ground, the water of crystallization in described salt hydrate crystal is foaming component, when being heated to closing
When thermophilic is spent, the water of crystallization vaporization in described salt hydrate crystal is sloughed, this solid-state junction
The process that brilliant water is converted into vaporous water steam and loses is supported knot of the present invention
The foam theory of brilliant hydrate foaming agent, by itself and polymer mixed, adds at polymer
During heat or thermo forming, the salt in described supported crystalline hydrate foaming agent
Water of crystallization in hydrate crystal vaporizes, and forms cryptomere cavity in polymer,
Thus realize foaming process, obtain polymer foams.
Additionally, the gain and loss of water of crystallization in described salt hydrate crystal and local environment temperature
Spending relevant, when temperature is higher, salt hydrate crystal is prone to dehydration process,
That is: the water of crystallization when polymer hot-working, in supported crystalline hydrate foaming agent
Vaporization is sloughed；When the temperature of the surroundings is low, salt hydrate crystal is prone to be formed
The process of water of crystallization, therefore after prepared polymer foams cooling, polymer
Water vapour in foamed materials foam structure can remain in foaming agent again in polymer
The hydrate of crystalline salt or crystalline salt re-forms salt hydrate crystal, again shape
Become described supported crystalline hydrate foaming agent, when described polymer foams again
When carrying out hot-working, may continue to foaming, therefore, described supported crystalline hydrate
Foaming agent has repetition foaming capacity.
In a preferred embodiment in accordance with the present invention, little when the granularity of described foaming agent
When 0.03 μm, the most easily fly upward, and be difficult to uniform with polymer mixed,
Usability is poor；When the granularity of foaming agent is more than 210 μm, use its polymerization prepared
Thing foamed materials hole is excessive, and material property is poor, therefore, and heretofore described load
The granularity changing crystalline hydrate foaming agent is 0.03～210 μm, preferably 0.1～100
μm, more preferably 0.3～30 μm.
The concrete component of described supported crystalline hydrate foaming agent is as described below:
Carrier, accounts for 100 parts in parts by weight.
In a preferred embodiment in accordance with the present invention, described carrier is hydrophilic but insoluble
One or more in the mineral powder of water, above-mentioned carrier can in aqueous medium all
Even dispersion, thus become nucleus and the crystal growth site of salt hydrate crystal.
Described carrier be water-insoluble nonmetal oxide, non-water soluble metal oxide,
One in non-water soluble metal hydroxide, non-water soluble metal salt and clay mineral
Or several, preferably one or more in clay mineral, described water-insoluble non-gold
Belonging to oxide and be preferably silicon dioxide, described non-water soluble metal oxide is preferably two
Titanium oxide, described non-water soluble metal hydroxide is preferably aluminium hydroxide, described non-
Water-soluble metal salt is preferably calcium carbonate, described clay mineral be preferably hydrotalcite powder,
One or more in potter's clay, Kaolin, montmorillonite and bentonite, above-mentioned carrier has
There is hydrophilic but water insoluble, can be dispersed in aqueous medium, thus become saline
The nucleus of solvate crystal and crystal growth site, and be easily obtained, low price, suitable
In large-scale industrial production.
In a preferred embodiment in accordance with the present invention, granularity is less than the carrier of 0.02 μm
Manufacturing cost is too high, is unsuitable for large-scale industrial production, and granularity is more than 200 μm
Carrier easily settles gathering, is difficult to suspended dispersed in aqueous medium, is not suitable as this
Carrier in invention, therefore, the granularity of heretofore described carrier is 0.02～200 μm,
Ensureing that carrier can be while even suspension be dispersed in aqueous medium, in order to provide more
Big specific surface area, the hydrate of induction crystalline salt or crystalline salt is heavy on its surface
Long-pending crystallization, thus form supported salt hydrate crystal, the granularity of described carrier is excellent
Elect 0.1～50 μm, more preferably 0.2～20 μm as.
Salt hydrate crystal, accounts for 1～100 part in parts by weight.
In a preferred embodiment in accordance with the present invention, described salt hydrate crystal is one
Plant inorganic salt hydrate crystal or the mixture of plurality of inorganic salt hydrate crystal, preferably
For the one in metal sulfate hydrate crystal and metal phosphate hydrate crystal or
Several, include but not limited to sodium sulfate, aluminum sulfate, aluminium potassium sulfate, copper sulfate, sulfur
Acid zinc, zinc sulfate ammonium, iron sulfate, ferrous sulfate, magnesium sulfate, sodium phosphate, phosphoric acid
Potassium, aluminum sodium phosphate, zinc phosphate, iron phosphate, ferrous phosphate, magnesium phosphate and magnesium phosphate
One or more in the hydrate crystal of ammonium, more preferably sodium sulfate, aluminum sulfate and
One or more in the hydrate crystal of aluminium potassium sulfate, wherein, salt hydrate crystal
Water of crystallization quantity in molecule is not specially limited.
In a preferred embodiment in accordance with the present invention, salt hydrate crystal and carrier
The performance of supported crystalline hydrate foaming agent is had a significant impact, according to weight by ratio
Number meter, when carrier accounts for 100 parts, if salt hydrate crystal is less than 1 part, foaming agent
Middle water content is too low, and foaming effect is poor；If salt hydrate crystal is more than 100 parts, saline
The salt hydrate crystal layer that solvate crystal is formed at carrier surface is blocked up, causes foaming agent
Dehydration temperature raise, supported effect weakens, and foaming effect is the best, and adds
The use cost of foaming agent.
In the range of the above-mentioned salt hydrate crystal part by weight with carrier, described carrier
The load capacity of the salt hydrate crystal on surface less, salt hydrate crystal layer the thinnest, institute
The dehydration temperature stating supported crystalline hydrate foaming agent is the lowest, has different dehydration temperature
The supported crystalline hydrate foaming agent of degree can meet the system of different polymer foams
Standby demand, range of application is wider.
According to the second aspect of the invention, it is provided that a kind of supported crystallization as above
The preparation method of hydrate foaming agent, the method comprises the following steps:
Step 1), by soluble in water for the hydrate of crystalline salt or crystalline salt, add
Carrier, stirring, obtain uniform dispersion liquid.
In a preferred embodiment in accordance with the present invention, step 1) described in crystalline salt
For gold can be preferably with one or more in the inorganic salt of water formation water-containing crystal salt
Belong to one or more in sulfate and metal phosphate, include but not limited to sodium sulfate,
Aluminum sulfate, aluminium potassium sulfate, copper sulfate, zinc sulfate, zinc sulfate ammonium, iron sulfate, sulfur
Acid ferrous iron, magnesium sulfate, sodium phosphate, potassium phosphate, aluminum sodium phosphate, zinc phosphate, phosphoric acid
One or more in ferrum, ferrous phosphate, magnesium phosphate and ammonium magnesium phosphate, more preferably
One or more in sodium sulfate, aluminum sulfate and aluminium potassium sulfate；Described crystalline salt
Hydrate is preferably the one in the hydrate of metal sulfate and metal phosphate or several
Kind, include but not limited to hydrated sulfuric acid sodium, hydrazine aluminum sulfate, 12 hydrazine aluminum sulfates
Potassium, copper sulfate pentahydrate, Zinc vitriol, zinc sulphate hydrate ammonium, a hydration sulfur
Acid ferrum, green vitriol, two Magnesium sulfate heptahydrates, five Magnesium sulfate heptahydrates, hydration
Sodium phosphate, three hypophosphite monohydrate potassium, four hypophosphite monohydrate aluminum sodium, Zinc phosphate tetrahydrate, two
Hypophosphite monohydrate ferrum, four hypophosphite monohydrate ferrous irons, three hydrated magnesium phosphates, five hypophosphite monohydrate enzymes
With one or more in six hydrated magnesium phosphate ammoniums, more preferably hydrated sulfuric acid sodium, water
Close one or more in aluminum sulfate and 12 hydrazine aluminum sulfate potassium.Above-mentioned crystalline salt
Or under conditions of the hydrate of crystalline salt is in aqueous medium and with the presence of nucleus, can be with
Water forms water-containing crystal salt, in the present invention, described crystalline salt or crystalline salt
Hydrate is in aqueous medium and under conditions of carrier exists, with described carrier for nucleus and
Crystal growth site, crystallizes at described carrier surface and grows, thus at the table of carrier
Face forms salt hydrate crystal layer.
In a preferred embodiment in accordance with the present invention, step 1) described in carrier be non-
Water solublity nonmetal oxide, non-water soluble metal oxide, non-water soluble metal hydrogen
One or more in oxide, non-water soluble metal salt and clay mineral, are preferably
One or more in clay mineral, described water-insoluble nonmetal oxide is preferably
Silicon dioxide, described non-water soluble metal oxide is preferably titanium dioxide, described non-
Water soluble metal hydroxide is preferably aluminium hydroxide, and described non-water soluble metal salt is excellent
Elect calcium carbonate as, described clay mineral be preferably hydrotalcite powder, potter's clay, Kaolin,
One or more in montmorillonite and bentonite, above-mentioned carrier has hydrophilic but insoluble
Yu Shui, can be dispersed in aqueous medium, thus becomes the nucleus of salt hydrate crystal
With crystal growth site, and it is easily obtained, low price, is suitable to large-scale industry raw
Produce.
The granularity of described carrier is 0.02～200 μm, and preferably 0.1～50 μm are more excellent
Elect 0.2～20 μm as, ensure carrier can even suspension be dispersed in aqueous medium same
Time, it is provided that bigger specific surface area, induction crystalline salt or the hydrate of crystalline salt
At its surface depositing crystalline, thus form supported salt hydrate crystal, and manufacture
Low cost, is suitable to large-scale industrial production.
In a preferred embodiment in accordance with the present invention, in parts by weight, step 1)
Described in the addition of carrier be 100 parts, described crystalline salt or the hydration of crystalline salt
The addition of thing is 1～100 part so that crystalline salt forms suitable thickness at carrier surface
The salt hydrate crystal layer of degree, it is ensured that containing suitable water of crystallization in prepared foaming agent
Content, foaming effect is good, and the dehydration temperature of foaming agent is relatively low, reduces and uses into
This.
Inventor also finds, in above-mentioned amount ranges, and can be by regulation preparation process
Middle carrier realizes preparing with the addition of crystalline salt or the hydrate of crystalline salt
The regulation of foaming agent dehydration temperature, adding of the hydrate of crystalline salt or crystalline salt
Entering amount the fewest, its salt hydrate crystal layer formed at carrier surface is the thinnest, prepares
The dehydration temperature of supported crystalline hydrate foaming agent is the lowest, can be according to practical situation system
For going out there is the supported crystalline hydrate foaming agent of different dehydration temperature, to meet not
Preparation demand with polymer foams.
In a preferred embodiment in accordance with the present invention, step 1) in for dissolve water
For general industry soft water, the addition of water is not specially limited so that crystalline salt or
The hydrate of crystalline salt is completely dissolved, and the stirring that can be well on after adding carrier
With dispersed.Step 1) can implement in room temperature, in order to accelerate crystalline salt
Or the dissolution velocity that the hydrate of crystalline salt is in water, hot water can be added or molten
Heating during solution, the temperature of hot water or heating is about 40～60 DEG C.
Step 2), be kept stirring for, to step 1) heating of the dispersion liquid that obtains, make moisture
Volatilization, obtains paste-like product.
In a preferred embodiment in accordance with the present invention, step 2) described in mixing speed
It is not specially limited, can guarantee that material can reach uniformly transfer heat during thermal dehydration
Mass transfer, owing to too high mixing speed can increase energy consumption, heretofore described stirs
Mix speed and be preferably 60～300 revs/min.
In a preferred embodiment in accordance with the present invention, step 2) middle heating dispersion liquid,
The moisture in dispersion liquid is made progressively to volatilize, crystalline salt or the water of crystalline salt in solution
The concentration of compound is stepped up, thus promotes it with described carrier as nucleus and crystal life
Long site, crystallizes at described carrier surface and grows, and forms salt hydrate crystal layer.
Step 2) in heating-up temperature the performance of prepared foaming agent is had a significant impact, due to boiling
Rise the foaming agent hydraulic performance decline that can cause preparing, therefore, ensureing that higher moisture is waved
While sending out speed, the heating-up temperature boiling point less than described dispersion liquid should be controlled, this
Bright step 2) in heating-up temperature be 40～120 DEG C, preferably 60～100 DEG C, more preferably
70 DEG C～95 DEG C.
In a preferred embodiment in accordance with the present invention, step 2) described in heat time heating time
Being not specially limited, concrete heat time heating time is closely related with heating-up temperature, to be had
There is certain fluidity and occur without the paste-like product hardened local for heating terminal.
Step 3), by step 2) the paste-like product heats that obtains dries, size-reduced,
Sieve, obtain described supported crystalline hydrate foaming agent.
In a preferred embodiment in accordance with the present invention, step 3) in by step 2)
The paste-like product heats arrived is dried, to remove amorphous free moisture and instability
Low heat-resisting water of crystallization, in order to ensure that described salt hydrate crystal is not sloughed because of drying
The heat-resisting water of crystallization of stable height, described heating, drying temperature should be not higher than 260 DEG C, this
Heating, drying temperature described in bright is 90～260 DEG C, preferably 100 DEG C～170 DEG C, more excellent
Elect 110～140 DEG C as.Described heating, drying process can be carried out in air dry oven.
In a preferred embodiment in accordance with the present invention, step 3) described in heating, drying
Time is not specially limited, and is no longer reduced to heating, drying terminal with weight of material.
In a preferred embodiment in accordance with the present invention, step 3) in dry after product
Thing carries out pulverizing, sieving, and the supported crystalline hydrate obtaining having suitable particle size is sent out
Infusion, the granularity of described foaming agent is 0.03～210 μm, preferably 0.1～100 μm,
More preferably 0.3～30 μm, are difficult to during use fly upward, it is easy to polymer mixed is equal
Even and suitable with its polymer foams pore size prepared, material property is good.
Described pulverizing and screen method are not specially limited, and can be commonly used in the art grinding
Mill, ball milling and vibration screening method etc..
According to the third aspect of the invention we, it is provided that a kind of supported crystallization as above
The application of hydrate foaming agent, it is characterised in that supported crystalline hydrate is foamed
Agent as additive application in the preparation of polymer foams.
Described supported crystalline hydrate foaming agent may be added to that for preparing polymer bubble
In the thermoplasticity of foam or thermosetting polymer, during polymer thermo forming,
The water of crystallization in salt hydrate crystal in described supported crystalline hydrate foaming agent is sent out
Raw vaporization, forms cryptomere cavity in polymer, thus realizes foaming process, obtain
Polymer foams.
According to the fourth aspect of the invention, it is provided that a kind of supported crystallization as above
The application process of hydrate foaming agent, the method comprises the following steps:
Step 1), by supported crystalline hydrate foaming agent, polymer and optional helping
Agent mixes, and obtains compositions.
In a preferred embodiment in accordance with the present invention, step 1) described in polymer be
One or more in thermoplastic polymer or thermosetting polymer, further, for
Thermoplastic polymer or heat for preparing polymer foams commonly used in the art
One or more in solidity polymer, described thermoplastic polymer includes but not limited to
Polrvinyl chloride or polymethyl methacrylate, described thermosetting polymer includes but does not limits
In phenolic resin or epoxy resin.
In a preferred embodiment in accordance with the present invention, step 1) described in supported knot
Brilliant hydrate foaming agent is not specially limited with the usage ratio of polymer, can be according to reality
Border expansion ratio needs arbitrarily to adjust, the usage ratio of the two if desired for higher
Expansion ratio, the consumption of supported crystalline hydrate foaming agent can be increased, as need relatively
Low expansion ratio, can reduce the consumption of supported crystalline hydrate foaming agent.
In a preferred embodiment in accordance with the present invention, step 1) described in polymer can
To be solid-state or liquid, solid-state includes lamellar, strip, graininess or powder, its
In, thermoplastic polymer is generally solid-state, and thermosetting polymer is generally liquid.Right
In lamellar, strip or granular polymer, can be by the mode such as mill or banburying
It being mixed with supported crystalline hydrate foaming agent, mixing temperature should be less than foaming agent
The dehydration temperature of middle water of crystallization, and ensure that polymer fully softens, great majority are gathered
Compound, preferred mixing temperature is 30～150 DEG C；For powder or the polymerization of liquid
Thing, can at room temperature directly mix it with supported crystalline hydrate foaming agent.
Described auxiliary agent is can to improve Polymer Processing performance or improve the polymer bubble prepared
The additive of foam material property, can be plasticizer commonly used in the art, stabilizer,
Lubricant, releasing agent etc., such as DOP (dioctyl phthalate), tribasic sulfur
Lead plumbate, calcium stearate, stearic acid, calcium carbonate etc..
Step 2), by step 1) heating of the compositions that obtains, and carry out processing and forming.
In a preferred embodiment in accordance with the present invention, step 2) in mix homogeneously
Supported crystalline hydrate foaming agent is carried out at a certain temperature with the compositions of polymer
Heating, the knot in salt hydrate crystal in described supported crystalline hydrate foaming agent
Brilliant water vaporizes, and forms cryptomere cavity, thus realize foaming process in polymer,
Obtain polymer foams.
In a preferred embodiment in accordance with the present invention, step 2) described in heating-up temperature
It is not specially limited, in the reasonable thermo forming temperature range of polymer and be higher than
The dehydration temperature of supported crystalline hydrate foaming agent, the heat being suitable in the present invention
Processing temperature is 140～260 DEG C, preferably 160～220 DEG C, more preferably 180～200 DEG C.
The method of described processing and forming is not specially limited, and can be commonly used in the art
Extrusion molding, injection moulding or compression molding etc..
Embodiment
Raw material used in the embodiment of the present invention and comparative example is purchase gained, tool
Body information is as follows:
Alumen (12 hydrazine aluminum sulfate potassium), Xi Long Chemical Co., Ltd.；
Aluminum sulfate, Aladdin Chemical trade company limited；
Bentonite (325 mesh), Shanghai ten thousand is according to Fine Chemical Co., Ltd；
Potter's clay (800 mesh), Guangzhou Di Cheng trade Co., Ltd；
Montmorillonite (800 mesh), Shanghai ten thousand is according to Fine Chemical Co., Ltd；
Nano silicon dispersion liquid (30nm, solid content 20%), Hangzhou ten thousand scape is new
Materials Co., Ltd；
Aluminium hydroxide (2000 mesh), Nanchong Chunfei Nano Crystalline-Silicon Technology Co., Ltd.；
Polyvinyl chloride resin powder (SG-5 type), Xinjiang Zhong Tai Chemical Co., Ltd.；
Heat cured liquid phenolic resin (moisture content 8%, viscosity 5000 centipoise), rarity
New material limited company.
The preparation of embodiment 1 alta-mud load Alumen foaming agent I
In the beaker that volume is 500mL, add 300mL deionized water and 40g is bright
Vitriol, is heated to 60～80 DEG C, and controlling mechanical agitation rotating speed is 100 revs/min, makes Alumen
It is completely dissolved.Weigh 60g bentonite, add in above-mentioned alum solution, with 300
Rev/min rotating speed stir 30 minutes, obtain uniform dispersion liquid.Rotating speed is down to 200
Rev/min, it is warming up to 95 DEG C and heats 60 minutes, make moisture evaporation, obtain paste-like and produce
Thing.Above-mentioned paste-like product is dried to constant weight at 110 DEG C, size-reduced, sieve
Described alta-mud load Alumen foaming agent I to powder.
Dehydration temperature and testing graininess, result is carried out according to method described in experimental example 1～2
It is shown in Table 1～2.
The preparation of embodiment 2 alta-mud load Alumen foaming agent II
In the beaker that volume is 500mL, add 300mL deionized water and 50g is bright
Vitriol, is heated to 60～80 DEG C, and controlling mechanical agitation rotating speed is 100 revs/min, makes Alumen
It is completely dissolved.Weigh 50g bentonite, add in above-mentioned alum solution, with 300
Rev/min rotating speed stir 30 minutes, obtain uniform dispersion liquid.Rotating speed is down to 200
Rev/min, it is warming up to 95 DEG C and heats 60 minutes, make moisture evaporation, obtain paste-like and produce
Thing.Above-mentioned paste-like product is dried to constant weight at 120 DEG C, size-reduced, sieve
Described alta-mud load Alumen foaming agent II to powder.
Dehydration temperature and testing graininess, result is carried out according to method described in experimental example 1～2
It is shown in Table 1～2.
The preparation of embodiment 3 potter's clay load Alumen foaming agent
In the beaker that volume is 500mL, add 300mL deionized water and 30g is bright
Vitriol, is heated to 60～80 DEG C, and controlling mechanical agitation rotating speed is 100 revs/min, makes Alumen
It is completely dissolved.Weigh 60g potter's clay, add in above-mentioned alum solution, with 300 turns/
Minute rotating speed stir 30 minutes, obtain uniform dispersion liquid.Rotating speed is down to 200
Rev/min, it is warming up to 90 DEG C and heats 80 minutes, make moisture evaporation, obtain paste-like and produce
Thing.Above-mentioned paste-like product is dried to constant weight at 100 DEG C, size-reduced, sieve
Described potter's clay to powder loads Alumen foaming agent.
Dehydration temperature and testing graininess, result is carried out according to method described in experimental example 1～2
It is shown in Table 1～2.
The preparation of embodiment 4 alta-mud load aluminum sulfate foaming agent
500mL deionized water and 60g aluminum sulfate is added in the beaker that volume is 1L,
Being heated to 60～80 DEG C, controlling mechanical agitation rotating speed is 100 revs/min, makes aluminum sulfate complete
CL.Weigh 60g bentonite, add in above-mentioned aluminum sulfate aqueous solution, with 300
Rev/min rotating speed stir 40 minutes, obtain uniform dispersion liquid.Rotating speed is down to 200
Rev/min, it is warming up to 95 DEG C and heats 100 minutes, make moisture evaporation, obtain paste-like
Product.Above-mentioned paste-like product is dried to constant weight at 130 DEG C, size-reduced, sieve
Obtain the described alta-mud load aluminum sulfate foaming agent of powder.
Dehydration temperature and testing graininess, result is carried out according to method described in experimental example 1～2
It is shown in Table 1～2.
The preparation of embodiment 5 bentonite-montmorillonite load Alumen foaming agent
In the beaker that volume is 1L, add 400mL deionized water and 50g Alumen, add
Heat is to 60～80 DEG C, and controlling mechanical agitation rotating speed is 150 revs/min, makes Alumen the most molten
Solve.Weigh 25g bentonite and 25g montmorillonite, add in above-mentioned alum solution,
Stir 40 minutes with the rotating speeds of 300 revs/min, obtain uniform dispersion liquid.By rotating speed
It is down to 250 revs/min, is warming up to 95 DEG C and heats 90 minutes, make moisture evaporation, obtain
Paste-like product.Above-mentioned paste-like product is dried to constant weight at 100 DEG C, size-reduced,
Sieve and obtain the described bentonite-montmorillonite load Alumen foaming agent of powder.
Dehydration temperature and testing graininess, result is carried out according to method described in experimental example 1～2
It is shown in Table 1～2.
The preparation of embodiment 6 nano silicon load Alumen foaming agent
200g silica dispersions and 35 is added in the beaker that volume is 500mL
G Alumen, is heated to 60～70 DEG C, and controlling mechanical agitation rotating speed is 100 revs/min, makes
Alumen is completely dissolved, and obtains uniform dispersion liquid.Rotating speed is risen to 300 revs/min,
It is warming up to 85 DEG C heat 120 minutes, makes moisture evaporation, obtain paste-like product.By upper
State paste-like product to dry to constant weight at 95 DEG C, size-reduced, sieving obtains powder
Described nano silicon load Alumen foaming agent.
Dehydration temperature and testing graininess, result is carried out according to method described in experimental example 1～2
It is shown in Table 1～2.
The preparation of embodiment 7 aluminium hydroxide load Alumen foaming agent
In the beaker that volume is 500mL, add 300mL deionized water and 40g is bright
Vitriol, is heated to 70～80 DEG C, and controlling mechanical agitation rotating speed is 100 revs/min, makes Alumen
It is completely dissolved.Weigh 50g aluminium hydroxide, add in above-mentioned alum solution, with 300
Rev/min rotating speed stir 40 minutes, obtain uniform dispersion liquid.Rotating speed is down to 200
Rev/min, it is warming up to 95 DEG C and heats 80 minutes, make moisture evaporation, obtain paste-like and produce
Thing.Above-mentioned paste-like product is dried to constant weight at 100 DEG C, size-reduced, sieve
Described aluminium hydroxide to powder loads Alumen foaming agent.
Dehydration temperature and testing graininess, result is carried out according to method described in experimental example 1～2
It is shown in Table 1～2.
The preparation of embodiment 8 RPVC foamed materials
By the prepared alta-mud load Alumen foaming agent I of embodiment 1, Corvic
Powder and other auxiliary agents mix according to following formula (in parts by weight) and charging sequence
Closing, mix 15 minutes in 1000 revs/min of high-speed stirred, discharging, room temperature place 24
Hour, then carry out extrusion processing.One, two, three, four sections of temperature of extruder are respectively
It being set to 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, extruder screw rotating speed is 25 turns/
Minute, the widest 40mm of mouth die, high 2mm, the type of cooling is air-cooled.Extrusion
Obtain the RPVC foam sheet that thickness is 3mm.
Formula:
Polyvinyl chloride resin powder, 100 parts；
DOP (dioctyl phthalate, plasticizer), 5 parts；
Lead sulfate tribasic, 2.5 parts；
Calcium stearate, 1 part；
Stearic acid, 0.5 part；
Calcium carbonate, 5 parts；
The foaming agent that embodiment 1 prepares, 15 parts.
Apparent density, expansion ratio and abscess is carried out according to method described in experimental example 3～4
Structured testing, the results are shown in Table 3～4.
The preparation of embodiment 9 soft PVC foamed materials
By the prepared alta-mud load Alumen foaming agent I of embodiment 1, Corvic
Powder and other auxiliary agents mix according to following formula (in parts by weight) and charging sequence
Closing, mix 15 minutes in 1000 revs/min of high-speed stirred, discharging, room temperature place 24
Hour, then carry out extrusion processing.One, two, three, four sections of temperature of extruder are respectively
It being set to 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, extruder screw rotating speed is 25 turns/
Minute, the widest 40mm of mouth die, high 2mm, the type of cooling is air-cooled.Extrusion
Obtain the described soft PVC foam sheet that thickness is 3.2mm.
Formula:
Polyvinyl chloride resin powder, 100 parts；
DOP (dioctyl phthalate, plasticizer), 30 parts；
Lead sulfate tribasic, 2.5 parts；
Calcium stearate, 1 part；
Stearic acid, 0.5 part；
Calcium carbonate, 5 parts；
The foaming agent that embodiment 1 prepares, 15 parts.
Apparent density, expansion ratio and abscess is carried out according to method described in experimental example 3～4
Structured testing, the results are shown in Table 3～4.
The preparation of embodiment 10 phenol formaldehyde foam
The alta-mud load Alumen foaming agent I that 20 parts of embodiments 1 are prepared and 100 parts of heat
Solidity liquid phenolic resin mixes, and mixes 15 minutes in 500 revs/min of high-speed stirred,
Then the material of above-mentioned mixing is added long 20cm, wide 20cm, the mould of high 5cm
In, in 185 DEG C of hot pressing 1 hour, take out after cooling, obtain described phenolic foam material.
The second heat processing of embodiment 11 RPVC foamed materials
Carry out pulverizing pelletize by implementing the 8 RPVC foamed materialss prepared, it is thus achieved that
Granularity is about the pellet of 2mm, then carries out secondary extrusion processing.Extruder one, two,
Three, four sections of temperature are respectively 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, extruder spiral shell
Bar rotating speed is 25 revs/min, the widest 40mm of mouth die, high 2mm, the type of cooling
For air-cooled.Extrusion obtains the RPVC foam sheet that thickness is 3.1mm.
According to method described in experimental example 3～4, prepare through second heat processing above-mentioned
RPVC foamed materials carries out apparent density, expansion ratio and foam structure and surveys
Examination, the results are shown in Table 3～4.
After above-mentioned second heat is processed, the RPVC foamed materials prepared
Expansion ratio is 1.47, slightly below the most hot worked expansion ratio；Abscess average
A diameter of 150 μm, slightly larger than processing prepared cell diameter first.Described hard gathers
Chloride foams material, after second heat is processed, still has foaming capacity, and has
Good foam structure, illustrates the supported crystalline hydrate foaming agent that the present invention provides
There is repetition foam characteristics.
Comparative example
The preparation of comparative example 1 unsupportedization pellet alum
Unsupportedization Alumen is prepared according to being similar to method described in the embodiment of the present invention 1
Granule, difference is, is added without bentonite, obtains described unsupportedization pellet alum,
Then according to method described in experimental example 1～2 carries out dehydration temperature and testing graininess, result
It is shown in Table 1～2.
The preparation of comparative example 2 unsupportedization aluminum sulfate granule
Unsupportedization sulphuric acid is prepared according to being similar to method described in the embodiment of the present invention 4
Alumina particles, difference is, is added without bentonite, obtains described unsupportedization aluminum sulfate
Granule, then according to method described in experimental example 1～2 carries out dehydration temperature and testing graininess,
The results are shown in Table 1～2.
The preparation of comparative example 3 bentonite clay particle
Bentonite clay particle, district is prepared according to being similar to method described in the embodiment of the present invention 1
It is not, is added without Alumen, obtain described bentonite clay particle, then according to experimental example
Described in 1～2, method carries out dehydration temperature and testing graininess, the results are shown in Table 1～2.
The preparation of comparative example 4 potter's clay granule
Potter's clay granule is prepared, difference according to being similar to method described in the embodiment of the present invention 3
It is, is added without Alumen, obtain described potter's clay granule, then according to experimental example 1～2
Described method carries out dehydration temperature and testing graininess, the results are shown in Table 1～2.
The preparation of comparative example 5 RPVC foamed materials
RPVC is prepared according to being similar to method described in the embodiment of the present invention 8
Foamed materials, difference is, swelling embodiment 1 used in embodiment 8 prepared
Soil load Alumen foaming agent replaces with the unsupportedization pellet alum that comparative example 1 prepares,
To described RPVC foamed materials, then according to method described in experimental example 3～4
Carry out apparent density, expansion ratio and foam structure test, the results are shown in Table 3～4.
Use the RPVC bubble that unsupportedization pellet alum prepares as foaming agent
Foam material has no foam structure, non-negative under polrvinyl chloride thermoplastic processing temperature is described
There is not dehydration in loadization pellet alum, without foam performance.
Experimental example
The dehydration temperature test of experimental example 1 foaming agent
Use differential scanning calorimetry (DSC) to the embodiment of the present invention 1～7 and comparative example
1～4 foaming agent prepared carry out dehydration temperature test, test sample weight: 4～8mg,
Test temperature: 100～300 DEG C, heating rate: 10 DEG C/min, nitrogen atmosphere, by
DSC curve heat absorption peak position determines water of crystallization dehydration temperature, and test result is as shown in table 1.
The water of crystallization dehydration temperature test result of table 1. foaming agent
As shown in table 1, the dehydration temperature of the unsupportedization pellet alum that comparative example 1 prepares
Peak value is 226 DEG C, and the supported Alumen formed through physical deposition on different carriers surface
Granule, i.e. by embodiment 1～3 and the foaming agent for preparing of embodiment 5～7, its dehydration temperature
Peak value is below 195 DEG C；
The dehydration temperature of the unsupportedization aluminum sulfate granule that comparative example 2 prepares is higher than
300 DEG C, and the supported aluminum sulfate formed through physical deposition at bentonite carrier surface
Grain, the foaming agent that i.e. embodiment 4 prepares, dehydration temperature peak value is down to 205 DEG C.
The explanation of above comparing result loads salt hydrate by physical deposition at carrier surface
The method of crystal can effectively reduce the dehydration temperature of crystalline hydrate, obtains dehydration temperature
Significantly reduced supported crystalline hydrate foaming agent.
Wherein, embodiment 1 and embodiment 2 use the method for the invention to prepare each group
Divide the alta-mud load Alumen foaming agent I and II that mass ratio is different, Alumen in embodiment 1
Being 2:3 with the weight ratio of bentonite carrier, the dehydration temperature peak value of prepared foaming agent is
180℃；The weight ratio of Alumen Yu bentonite carrier is risen to 1:1 by embodiment 2, system
The dehydration temperature peak value of the foaming agent obtained is increased to 193 DEG C.As can be seen here, carrier is reduced
The load capacity of surface salt hydrate crystal can reduce prepared supported hydrate crystal and send out
The dehydration temperature of infusion, on this basis, can by regulation preparation process in carrier with
The addition of the hydrate of crystalline salt or crystalline salt realizes prepared foaming agent
The regulation of dehydration temperature.
Comparative example 3 and comparative example 4 prepared carrier bentonite and potter's clay granule, at DSC
Test is warming up to 300 DEG C dehydration endothermic peak does not occurs all the time, illustrate that carrier itself is acomia
Bubble effect.
The testing graininess of experimental example 2 foaming agent
Use BIC laser particle analyzer (Zeta PLAS, Brookhaven Instruments
Cooperation, USA) or Malvern laser particle analyzer to the embodiment of the present invention 1～7 He
The foaming agent that comparative example 1～4 prepares carries out testing graininess, uses dehydrated alcohol for dispersion
Liquid, method includes: take 3mg foaming agent sample, adds 5mL dehydrated alcohol, shakes up
Obtain suspension afterwards, take the above-mentioned suspension of 2mL and be placed in detection cell, measure under room temperature
The particle mean size of sample, test result is as shown in table 2.
The testing graininess result of table 2. foaming agent
The apparent density test of experimental example 3 polymer foams
By embodiment 8～11 and the polymer foams for preparing of comparative example 5 cut established practice
Cuboid sample then, accurately measures the long l of sample, wide w, high h, and weighs sample
Weight m, be calculated as follows apparent density and the foaming of polymer foams
Multiplying power, result is as shown in table 3.
The apparent density of the density/polymer foams of expansion ratio=polymer
The apparent density test result of table 3. polymer foams
The foam structure observation of experimental example 4 foam of polymers foam material
Use scanning electron microscope (HITACHIS-470, Hitachi) to embodiment
8～11 and the foam structure of polymer foams for preparing of comparative example 5 be observed, survey
The average diameter of amount abscess, result is as shown in table 4.
The cell diameter test result of table 4. polymer foams
Above in association with preferred implementation and exemplary example, the present invention is carried out in detail
Explanation.But it is to be understood that, these detailed description of the invention are only to the present invention
Illustrative explanations, does not constitute any restriction to protection scope of the present invention.Do not surpassing
In the case of going out spirit and scope of the present invention, can to the technology of the present invention content and
Its embodiment carries out various improvement, equivalencing or modification, and these each fall within this
In bright protection domain.Protection scope of the present invention is as the criterion with claims.
Claims (10)
1. a supported crystalline hydrate foaming agent, it is characterised in that this foaming agent
Including: carrier and the salt hydrate crystal being carried on carrier surface.
Supported crystalline hydrate foaming agent the most according to claim 1, it is special
Levy and be,
In parts by weight, described carrier accounts for 100 parts, and described salt hydrate crystal accounts for
1～100 part, and/or
Described carrier is the one or several in hydrophilic but water-fast mineral powder
Kind, further, for water-insoluble nonmetal oxide, non-water soluble metal oxidation
In thing, non-water soluble metal hydroxide, non-water soluble metal salt and clay mineral
One or more, preferably one or more in clay mineral, described water-insoluble
Nonmetal oxide is preferably silicon dioxide, and described non-water soluble metal oxide is preferred
For titanium dioxide, described non-water soluble metal hydroxide is preferably aluminium hydroxide, institute
Stating non-water soluble metal salt and be preferably calcium carbonate, described clay mineral is preferably brucite
One or more in powder, potter's clay, Kaolin, montmorillonite and bentonite, and/or
The granularity of described carrier is 0.02～200 μm, and preferably 0.1～50 μm are more excellent
Elect 0.2～20 μm as, and/or
Described salt hydrate crystal is a kind of inorganic salt hydrate crystal or plurality of inorganic salt
The mixture of hydrate crystal, preferably metal sulfate hydrate crystal and metal phosphorus
One or more in hydrochloride hydrates crystal, more preferably sodium sulfate, aluminum sulfate and
One or more in the hydrate crystal of aluminium potassium sulfate.
Supported crystalline hydrate foaming agent the most according to claim 1 and 2, its
Being characterised by, the granularity of described supported crystalline hydrate foaming agent is 0.03～210
μm, preferably 0.1～100 μm, more preferably 0.3～30 μm.
4. the supported crystalline hydrate as described in one of claims 1 to 3 is sent out
The preparation method of infusion, it is characterised in that the method includes:
Step 1), by soluble in water for the hydrate of crystalline salt or crystalline salt, add
Carrier, stirring, obtain uniform dispersion liquid；
Step 2), be kept stirring for, to step 1) heating of the dispersion liquid that obtains, make moisture
Volatilization, obtains paste-like product；
Step 3), by step 2) the paste-like product heats that obtains dries, size-reduced,
Sieve, obtain described supported crystalline hydrate foaming agent.
The preparation of supported crystalline hydrate foaming agent the most according to claim 4
Method, it is characterised in that
Step 1) described in crystalline salt be can with water formed water-containing crystal salt inorganic salt
In one or more, preferably the one in metal sulfate and metal phosphate or
Several, more preferably one or more in sodium sulfate, aluminum sulfate and aluminium potassium sulfate,
And/or
Step 1) described in carrier be according to the material described in claim 2, described load
Body has granularity according to claim 2, and/or
Step 1) in, in parts by weight, the addition of described carrier is 100 parts,
The addition of the hydrate of described crystalline salt or crystalline salt is 1～100 part.
6. according to the supported crystalline hydrate foaming agent described in claim 4 or 5
Preparation method, it is characterised in that
Step 2) described in heating-up temperature be 40～120 DEG C, preferably 60～100 DEG C, more
It is preferably 70～95 DEG C.
7. foam according to the supported crystalline hydrate one of claim 4 to 6 Suo Shu
The preparation method of agent, it is characterised in that
Step 3) in by step 2) the paste-like product heats that obtains dries to constant weight,
And/or
Step 3) described in dry temperature be 90～260 DEG C, preferably 100～170 DEG C,
More preferably 110～140 DEG C, and/or
Step 3) in the supported crystalline hydrate foaming agent that obtains have and want according to right
Seek the granularity described in 3.
8. the supported crystalline hydrate as described in one of claims 1 to 3 is sent out
The application of infusion, it is characterised in that using supported crystalline hydrate foaming agent as adding
Add agent and be applied to the preparation of polymer foams.
9. a supported crystalline hydrate foaming agent as claimed in claim 8 should
By method, it is characterised in that the method includes:
Step 1), by supported crystalline hydrate foaming agent, polymer and optional helping
Agent mixes, and obtains compositions；
Step 2), by step 1) heating of the compositions that obtains, and carry out processing and forming.
Answering of supported crystalline hydrate foaming agent the most according to claim 9
By method, it is characterised in that
Step 1) described in polymer be in thermoplastic polymer or thermosetting polymer
One or more, and/or
Step 2) described in heating-up temperature be 140～260 DEG C, preferably 160～220 DEG C,
More preferably 180～200 DEG C.
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Cited By (1)
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| EP3741799A1 (en) | 2019-05-21 | 2020-11-25 | Nabaltec AG | Method for producing a polymer foam |
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| GB903564A (en) * | 1959-12-10 | 1962-08-15 | Dow Chemical Co | Process for making foamed styrene polymers |
| GB1403808A (en) * | 1972-03-30 | 1975-08-28 | Charbonnages Ste Chimique | Manufacture of articles of cellular thermoplastic material |
| CN1091456A (en) * | 1990-06-15 | 1994-08-31 | 俄罗斯科学院西伯利亚分院催化剂研究院 | Heat-storing material and uses thereof |
| CN1610579A (en) * | 2002-08-19 | 2005-04-27 | Lg化学株式会社 | Hydrocarbon steam cracking catalyst for olefin preparation, method for preparing the same, and olefin preparation method using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB903564A (en) * | 1959-12-10 | 1962-08-15 | Dow Chemical Co | Process for making foamed styrene polymers |
| GB1403808A (en) * | 1972-03-30 | 1975-08-28 | Charbonnages Ste Chimique | Manufacture of articles of cellular thermoplastic material |
| CN1091456A (en) * | 1990-06-15 | 1994-08-31 | 俄罗斯科学院西伯利亚分院催化剂研究院 | Heat-storing material and uses thereof |
| CN1610579A (en) * | 2002-08-19 | 2005-04-27 | Lg化学株式会社 | Hydrocarbon steam cracking catalyst for olefin preparation, method for preparing the same, and olefin preparation method using the same |
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| EP3741799A1 (en) | 2019-05-21 | 2020-11-25 | Nabaltec AG | Method for producing a polymer foam |
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