CN109535745A - A kind of refrigerator sealing strip thermoplastic elastic material and preparation method thereof - Google Patents
A kind of refrigerator sealing strip thermoplastic elastic material and preparation method thereof Download PDFInfo
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- CN109535745A CN109535745A CN201811399614.6A CN201811399614A CN109535745A CN 109535745 A CN109535745 A CN 109535745A CN 201811399614 A CN201811399614 A CN 201811399614A CN 109535745 A CN109535745 A CN 109535745A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
- C08L91/06—Waxes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
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Abstract
The invention belongs to thermoplastic elastic material fields, and in particular to a kind of refrigerator sealing strip thermoplastic elastic material and preparation method thereof.The refrigerator sealing strip thermoplastic elastic material, by weight, including following components: SEBS20~45 part；30~55 parts of paraffin oil；10~40 parts of polypropylene；2~15 parts of the mixture of molecular sieve, silica and titanium dioxide；Wherein, the mixture of the molecular sieve, silica and titanium dioxide is to first pass through fatty acid modified, load silver ion again mixture.Compared with prior art, the thermoplastic elastic material tensile strength of the application, elongation at break are greatly improved；And the elastomeric material processing technology is simple, surface is fine and smooth, and good hand touch, bacteria can be prevented from growing.
Description
Technical field
The invention belongs to thermoplastic elastic material fields, and in particular to a kind of refrigerator sealing strip thermoplastic elastomer (TPE) material
Material and preparation method thereof.
Background technique
Sealing strip always is the hot spot of research as one of an important factor for maintaining internal temperature of refrigerator.The first generation
Refrigerator sealing strip product is thermoset elastomer materials, it has high temperature resistant, oil resistant, solvent resistant, compression set low etc. all
More advantages, but there is difficult coloring, processing difficulties and expendable disadvantage.Second generation refrigerator sealing strip product is PVC material
Material, PVC is a kind of extraordinary material, because it is durable, cheap, degradation with aging is very slow, stable chemical performance, neutrality, nothing
Poison.However due to the feature of environmental protection problem of PVC sealing strip, the harmfulness and PVC of PVC sealing strip process and post-processing make
With the defects of lower temperature resistance is poor in the process, it is greatly limited the application of PVC sealing strip.Third generation refrigerator seals web
The shortcomings that material, there is this or that in view of the first, second generation material, third generation thermoplastic elastic material comes into being, this
The novel thermoplastic elastic material of kind, becomes a developing direction of third generation refrigerator sealing strip material.
Thermoplastic elastomer (TPE), abbreviation TPE or TPR are the abbreviations of Thermoplastic rubber.It is that there is rubber under room temperature
The elasticity of glue has the molding a kind of elastomer of plasticization under high temperature.Thermoplastic elastomer (TPE) is structurally characterized in that by chemical bond group
At different resin sections and rubber segments, resin section forms physics crosslinking points by inter-chain action power, and rubber segments are high resiliency segments,
Contribution elasticity.The physical crosslinking variation with temperature of plastics section and be in reversible change, it is shown that the plastics of thermoplastic elastomer (TPE) add
Work characteristic.
Although elastic body material for refrigerator sealing strips has preferable low-temperature stability, other performances, such as hardness is drawn
It is all less desirable to stretch intensity, breaking strength.And during use, it is easier dirty, Yi Zisheng bacterium makes in this way
The food being placed in refrigerator cannot ensure.
Summary of the invention
In order to solve the above-mentioned technical problem, the first aspect of the invention provides a kind of refrigerator sealing strip thermoplastic elastomehc
Elastomer material, by weight, including following components:
20~45 parts of SEBS；
30~55 parts of paraffin oil；
10~40 parts of polypropylene；
2~15 parts of the mixture of molecular sieve, silica and titanium dioxide；
Wherein, the mixture of the molecular sieve, silica and titanium dioxide be first pass through it is fatty acid modified, load silver again
The mixture of ion.
As a kind of perferred technical scheme, the shore hardness of the SEBS is 50~80A.
As a kind of perferred technical scheme, the dynamic viscosity of the paraffin oil is 80~200mm2/s。
As a kind of perferred technical scheme, the polypropylene is respectively 5~20g/10min's by melt flow rate (MFR)
One or more polypropylene compositions.
As a kind of perferred technical scheme, the polypropylene by melt flow rate (MFR) be respectively 5~10g/10min and
The polypropylene of 11~20g/10min forms.
As a kind of perferred technical scheme, the average grain diameter of the molecular sieve be 500~800nm, silica it is flat
Equal partial size is 100~300nm, the average grain diameter of titanium dioxide is 10~50nm.
As a kind of perferred technical scheme, molecular sieve in the mixture of the molecular sieve, silica and titanium dioxide,
The weight percent of silica, titanium dioxide are as follows:
Molecular sieve 40~55%；
Silica 30~40%；
Titanium dioxide remainder amount.
As a kind of perferred technical scheme, the mixture of the molecular sieve, silica and titanium dioxide is to first pass through
Fatty acid modified, load silver ion again the mixture that carbon atom number is 8~16.
As a kind of perferred technical scheme, the mixture of the molecular sieve, silica and titanium dioxide is to first pass through
Fatty acid modified, load silver ion again the mixture that carbon atom number is 8~12.
The second aspect of the invention provides the preparation method of the thermoplastic elastic material, including following step
It is rapid:
S1 weighs raw material by above-mentioned parts by weight；
SEBS and paraffin oil are mixed 40~60min by S2 in blender, and polypropylene, molecular sieve, titanium dioxide is then added
The mixture of silicon and titanium dioxide is mixed together 40~60min, obtains pre-composition；
S3 by pre-composition described in step S2 be placed in double screw extruder squeeze out, pelletizing to get.
The utility model has the advantages that compared with prior art, the thermoplastic elastic material tensile strength of the application, elongation at break obtain
To large increase；And the elastomeric material processing technology is simple, surface is fine and smooth, and good hand touch, bacteria can be prevented from growing.
Specific embodiment
For the purpose of following detailed description, it should be understood that the present invention can be used various substitutions variation and step it is suitable
Sequence, unless specifically stated on the contrary.In addition, above range is considered as continuously, and including this when a numberical range disclosed herein
Each value between the minimum value and maximum value and this minimum value and maximum value of range.Further, when range refers to
Each integer when integer, between minimum value and maximum value including the range.In addition, when providing multiple range Expressive Features
Or when characteristic, the range can be merged.In other words, unless otherwise specified, otherwise all ranges disclosed herein should be understood that
Being includes any and all subrange being wherein included into.For example, should be regarded as including minimum value from the specified range of " 1 to 10 "
Any and all subrange between 1 and maximum value 10.The Exemplary range of range 1 to 10 include but is not limited to 1 to
6.1,3.5 to 7.8,5.5 to 10 etc..
To solve the above-mentioned problems, the present invention provides a kind of refrigerator sealing strip thermoplastic elastic materials, by weight
Part meter, including following components:
20~45 parts of SEBS；
30~55 parts of paraffin oil；
10~40 parts of polypropylene；
2~15 parts of the mixture of molecular sieve, silica and titanium dioxide；
Wherein, the mixture of the molecular sieve, silica and titanium dioxide be first pass through it is fatty acid modified, load silver again
The mixture of ion.
As a preferred embodiment, the refrigerator sealing strip thermoplastic elastic material, by weight, packet
Include following components:
30 parts of SEBS；
40 parts of paraffin oil；
Polipropene 25 part；
10 parts of the mixture of molecular sieve, silica and titanium dioxide；
Wherein, the mixture of the molecular sieve, silica and titanium dioxide be first pass through it is fatty acid modified, load silver again
The mixture of ion.
SEBS
In the application, term " SEBS " refers to the Ethylene/Butylene using polystyrene as end segment, obtained with polybutadiene plus hydrogen
Copolymer is the linear tri-block copolymer of intermediate elastic block.The molecular structure of SEBS is illustrated are as follows:
SEBS is the three block that molecule is configured as A-B-A
Copolymer.Wherein, A refers to polystyrene section, and B refers to Ethylene/Butylene section.The polystyrene section of SEBS is stiff plastic block, ethylene-fourth
Alkene section is elastomeric blocks, and the glass transition temperature of hard plastic shape block is 100 DEG C, and the glass transition temperature of elastomeric blocks is -50 DEG C.
Applicants have discovered that under room temperature both blocks be each other thermodynamically it is incompatible, to generate two-phase knot
Structure is in micron-scale phase separation state.Polystyrene section be scattered in Ethylene/Butylene formation rubber phase in, and with Ethylene/Butylene section
Form physical cross-linked network.With increasing for polystyrene content, distribution of the polystyrene section in Ethylene/Butylene becomes from threadiness
For reticular structure.
As a preferred embodiment, the shore hardness of the SEBS is 50~80A.
Preferably, the shore hardness of the SEBS is 60~77A.
Shore hardness is also known as shore a hardness.Indicate metal, plastics, rubber material hardness level a kind of method.It resists outer
The ability of power indentation is hardness, the soft or hard degree of the size reflection material of numerical value.Reference standard GB/T531-1999, uses Shao
It when your hardometer is measured, is pressed on the surface of sample with scleroscopic pressing, measures the depth of pressing pressing in sample.Pressing
Compression distance is deeper, illustrates that hardness is smaller, and scleroscopic pointer directly displays out the hardness of rubber.Shao Er hardness is divided into A type, B
Type, c-type, four kinds of D type, A type is for measuring soft rubber, c-type and D type for measuring half-hard rubber and hard rubber, A, B, C, D type
For measuring plastics.
As a preferred embodiment, the average molecular weight of the SEBS is 2~400,000.
Preferably, the average molecular weight of the SEBS is 16~400,000.
Paraffin oil
Paraffin oil, also known as white oil, mineral oil, colourless, tasteless, chemical inertness, light stability can be good.Basic group of white oil
It is white through dewaxing, carbonization, neutralization, activity from the high boiling fraction (i.e. lube cut) of petroleum fractionating as saturated hydrocarbon structure
It is formed after the processing such as soil purification, is the mixture of liquid type hydro carbons, main component is the mixing of the positive isoparaffin of C16~C31
Object, the substances such as aromatic hydrocarbon, nitrogenous, oxygen, sulphur are similar to zero.White oil has good oxidation stability, chemical stability, and light is stabilized
Property.
As a preferred embodiment, the dynamic viscosity of the paraffin oil is 50~500mm2/s。
Preferably, the dynamic viscosity of the paraffin oil is 80~300mm2/s。
It is highly preferred that the dynamic viscosity of the paraffin oil is 80~200mm2/s。
In the application, the dynamic viscosity of paraffin oil is measured with reference to the method for GB/T265-1988.Determination step is at 40 DEG C
Under, the paraffin oil of certain volume flows through the time for the glass capillary viscometer that one has been demarcated, the hair of viscosmeter under gravity
The product of tubule constant and flowing time, the dynamic viscosity of paraffin oil at as 40 DEG C.
Polypropylene
Polypropylene is a kind of thermoplastic resin as prepared by propylene polymerization.It is divided into isotactic poly- third by methyl arrangement position
Alkene, random polypropylene and three kinds of syndiotactic polypropylene.The same side that methyl is arranged in molecular backbone claims isotactic polypropylene, if methyl without
The two sides for being arranged in molecular backbone of order claim random polypropylene, advise between the two sides that methyl is arranged alternately in molecular backbone claim poly-
Propylene.Polypropylene is also including the copolymer of propylene and a small amount of ethylene.Usually translucent colorless solid is odorless nontoxic.By
In compound with regular structure and highly crystallized, therefore fusing point may be up to 167 DEG C.Heat-resisting, corrosion-resistant, product can be its protrusion with moise-heat sterilization
Advantage.Density is small, is most light general-purpose plastics.The disadvantage is that low-temperature impact resistance is poor, it is more easy to aging.
Polypropylene in the application has lower heat distortion temperature, low transparency, low-luster, low rigidity, strong anti-impact
Hit intensity, crystallinity is higher, and surface rigidity and anti-scratch characteristic are fine, environmental stress resistance.
As a preferred embodiment, the polypropylene is respectively 5~20g/10min's by melt flow rate (MFR)
One or more polypropylene compositions.
Preferably, the polypropylene is respectively the poly- of 5~10g/10min and 11~20g/10min by melt flow rate (MFR)
Propylene composition.
In the present invention, polyacrylic melt flow rate (MFR) refers to 3682 standard testing of GB/T.It characterizes thermoplastic polymer
Melt flowability, also reflect molecular weight and its distribution, the crosslinking degree and processing performance of polymer.Applicants have discovered that
For same resin, when its molecular weight is larger, there is lesser melt index.This is because when molecular weight is larger, phase
That answers has longer molecular chain structure, and when resin is in a molten state, longer molecular entanglement is serious, dyskinesia,
Biggish system viscosity is shown, also shows biggish highest flowing torque and balance flowing torque accordingly.Work as molecular weight
Hour, just on the contrary, strand is shorter, movement is easy situation, and system shows lesser viscosity and lesser torque.
The mixture of molecular sieve, silica and titanium dioxide
In the application, the mixture filler that molecular sieve, silica and titanium dioxide is added can be to thermoplastic elastomer (TPE)
Apparent reinforcing effect is played, while the hardness and permanent compression set of thermoplastic elastic material can also be improved.
As a preferred embodiment, the mixture of the molecular sieve, silica and titanium dioxide is to first pass through
Fatty acid modified, load silver ion again mixture.
As a preferred embodiment, the average grain diameter of the molecular sieve is 500~800nm, silica it is flat
Equal partial size is 100~300nm, the average grain diameter of titanium dioxide is 10~50nm.
As a preferred embodiment, the average grain diameter of the molecular sieve is 600~800nm, silica it is flat
Equal partial size is 100~200nm, the average grain diameter of titanium dioxide is 10~30nm.
In the application, the average grain diameter of the molecular sieve, silica and titanium dioxide is by using NANOTRAC particle
Size distribution analysis is obtained by the diameter of dynamic light scattering method measurement particle.
In the application, the molecular sieve is a kind of artificial synthesized hydrated aluminosilicate or day with screening molecular action
Right zeolite.Its chemical general formula is (M '2M)O·Al2O3·xSiO2·yH2O, M ', M are respectively monovalence, bivalent cation such as K+、Na+And Ca2+、Ba2+Deng.There are many duct of uniform pore diameter and the hole of marshalling, the molecular sieves of different pore size in structure for it
Different sizes and shapes molecule is separated.
As a preferred embodiment, the molecular sieve is Titanium Sieve Molecular Sieve.
The Titanium Sieve Molecular Sieve is that Ti atomic component replaces the aluminium atom in Si-Al molecular sieve to form, and belongs to ZSM-5 series
Zeolite molecular sieve.The Titanium Sieve Molecular Sieve is to be connected by the primary structure units such as oxygen-octahedron and titanyl tetrahedron by oxygen bridge
It connects, constitutes pentacyclic secondary structure unit, and be further formed three-dimensional microporous framework.
In the application, the silica can by it is commercially available acquisition and also make by oneself to obtain.
As a preferred embodiment, the preparation step of the silica are as follows:
(1) the saturation ammonium hydroxide that 44mL dehydrated alcohol, 2~18mL are sequentially added in flask, stirs evenly；
(2) 1~4mL ethyl orthosilicate is taken to be slowly added in flask, speed 2.5mL/h, after being added dropwise to complete, the reaction was continued
1~2h.After reaction, it is centrifuged, obtains silica.
In the application, the titanium dioxide is a kind of polycrystalline compounds, and particle is in regularly arranged.Its chemical property is extremely
Stablize, is a kind of amphoteric oxide of slant acidity.Hardly reacted with other elements and compound under room temperature, to oxygen, ammonia, nitrogen,
Hydrogen sulfide, carbon dioxide, sulfur dioxide all do not work, not soluble in water, fatty, are also insoluble in diluted acid and inorganic acid, alkali, only molten
In hydrofluoric acid.
Titanium dioxide in the application can be prepared by sulfuric acid process.The sulfuric acid process refers to using sulfuric acid as production titanium dioxide
The primary raw material of titanium first has to obtain titanium sulfate solution, through restoring the most of impurity iron member removed in solution with vacuum crystallization
Element；By the way that titanium liquid is heated to temperature close to boiling, titanium sulfate solution is hydrolyzed, metatitanic acid precipitating is obtained；By metatitanic acid
Precipitating filtering, removes most spent acid and harmful metal impurity；Again through one to secondary washing, the overwhelming majority in metatitanic acid is removed
Impurity metallic elements；Salt treatment agent appropriate is added into metatitanic acid, and after filtering and removing major part water, metatitanic acid filter cake enters
Brickkiln calcining, obtains titanium dioxide first product.After post treatment by the above first product, titanium dioxide product is obtained.
Titanium dioxide in the application can also be prepared by chloridising.The chloridising is the side using chlorine as primary raw material
Method.The ferro element in ilmenite first is removed with hydrochloric acid or smelting, obtains the very high titanium material of Ti content；Then by coke and chlorine
It reacts with titanium material and generates titanium tetrachloride；After heated purification, react to obtain rutile-type dioxy at high temperature with oxygen
Change titanium first product.The above first product after post treatment, obtains titanium dioxide product.
Titanium dioxide in the application is also commercially available.
In the application, by SEBS and polyacrylic synergistic effect, obtained thermoplastic elastic material has many excellent
Point.But polypropylene is a kind of material that melt strength is poor, in the case where squeezing out profile, dimensional accuracy is difficult to control, and does
Product thickness out is inhomogenous, and surface sophistication is bad.Applicants have discovered that the molecular sieve of different-grain diameter, titanium dioxide is added
Silicon and titanium dioxide improve the fine and smooth degree of thermoplastic elastic material by the synergistic effect of different-grain diameter.Analysis may
The reason of be: molecular sieve, silica and the titanium dioxide of one side different-grain diameter are filled up to be formed not in SEBS and polypropylene
With in the bubble and cavity blemish of size, then relatively small partial size progress is secondary, fills up three times.Especially molecular sieve is flat
Equal partial size is 500~800nm, the average grain diameter of silica is 100~300nm, the average grain diameter of titanium dioxide be 10~
When 50nm, the dimensional accuracy of thermoplastic elastomer (TPE), surface exquisiteness sense can be effectively controlled.When the size of three kinds of inorganic fillers
Range is not in corresponding particle size range, then without this effect.
Applicants have discovered that improve thermoplastic elastomer (TPE) mechanical property and material surface exquisiteness sense simultaneously, and effectively
Elastomeric material aging is prevented, the molecular sieve, silica, the weight percent of titanium dioxide are particularly significant.Due to being related to
Influence factor it is more, applicant conjecture the possible reason is, one side thermoplastic elastomer system is with molecular sieve, titanium dioxide
Centered on silicon, titanium dioxide, adsorb melt in macromolecular chain ordered arrangement formed nucleus, be conducive to polyacrylic out-phase at
Core reduces the hardness of thermoplastic elastic material；On the other hand, the crystal grain that the filler of different-grain diameter is formed is different, if not
The dosage of three can be controlled well, is closely piled up between the crystal grain of formation, and mutually crowded, crystal form becomes not perfect；In addition, point
Sub- sieve, silica, titanium dioxide hardness with higher, can be improved the hardness of composite material.Many factors influence each other,
It mutually restricts, therefore the weight percent of molecular sieve, silica, titanium dioxide is particularly significant.
As a preferred embodiment, molecular sieve in the mixture of the molecular sieve, silica and titanium dioxide,
The weight percent of silica, titanium dioxide are as follows:
Molecular sieve 40~55%；
Silica 30~40%；
Titanium dioxide remainder amount.
Preferably, molecular sieve, silica, titanium dioxide in the mixture of the molecular sieve, silica and titanium dioxide
The weight percent of titanium are as follows:
Molecular sieve 50%；
Silica 35%；
Titanium dioxide 15%.
As a preferred embodiment, the mixture of the molecular sieve, silica and titanium dioxide is to first pass through
Fatty acid modified, load silver ion again the mixture that carbon atom number is 8~16.
As a preferred embodiment, the mixture of the molecular sieve, silica and titanium dioxide is to first pass through
Fatty acid modified, load silver ion again the mixture that carbon atom number is 8~12.
In the application, the mixture of the molecular sieve, silica and titanium dioxide first pass through it is fatty acid modified, load again
The specific preparation step of silver ion are as follows:
(1) molecular sieve, silica, titanium dioxide are added to absolute ethanol, ultrasound；
(2) mixture in step (1) is heated to 80 DEG C, speed of agitator 400rpm is condensed back simultaneously.Then plus
Enter the dispersion liquid containing fatty acid, after continuous heating 4~for 24 hours, centrifugation obtains fatty acid modified mixture；
(3) the fatty acid modified mixture for taking 10g step (2) to obtain is added to 50~200mL 0.1mol/L's
AgNO3In solution, at 60 DEG C react 4~6h, filtering to get.
Wherein, in step (1) parts by weight of dehydrated alcohol be molecular sieve, silica, titanium dioxide total weight parts
Five times.
The parts by weight for the fatty acid being added in step (2) are the 1 of the total weight parts of molecular sieve, silica, titanium dioxide
~50%.
Although molecular sieve, silica and titanium dioxide filler, which is added, can improve the mechanical property of thermoplastic elastomer (TPE),
But since the dispersibility of inorganic particulate in the polymer is poor, limit the content of inorganic filler.By fatty acid to molecule
Sieve, silica, titanium dioxide are modified, and improve the dispersibility of inorganic particulate in the polymer.The applicant surprisingly sends out
Existing, jointly through fatty acid modified after three's mixing, obvious to the improvement of thermoplastic elastomer (TPE), individually modification remixes effect
Fruit is poor.
And due to the hole configurations of inorganic particulate itself, the silver ion with bactericidal effect, silver ion energy can be adsorbed
It is enough adsorbed on bacterium surface, or even to intracellular penetration, in conjunction with the protein of bacterium, precipitates bacterio protein；Silver ion
For strong adsorption in bacterium surface, the enzyme for playing respiration that bacterium relies makes it become to lose breathing work by turning property of silver ion catalysis
Microorganism, to provide certain cleaning guarantee to the food in refrigerator.In addition, by fatty acid modified back loading silver from
Son, part silver ion is distributed on fatty acid chain, and after being added to polymer, silver ion more evenly can be dispersed in thermoplastic elastic
In body material.
The preparation method of the thermoplastic elastic material, which comprises the following steps:
S1 weighs raw material by above-mentioned parts by weight；
SEBS and paraffin oil are mixed 40~60min by S2 in blender, and polypropylene, molecular sieve, titanium dioxide is then added
The mixture of silicon and titanium dioxide is mixed together 40~60min, obtains pre-composition；
S3 by pre-composition described in step S2 be placed in double screw extruder squeeze out, pelletizing to get.
The present invention is specifically described below by embodiment.It is necessarily pointed out that following embodiment is only used
In the invention will be further described, it should not be understood as limiting the scope of the invention, professional and technical personnel in the field
The some nonessential modifications and adaptations made according to the content of aforementioned present invention, still fall within protection scope of the present invention.
In addition, if without other explanations, it is raw materials used to be all commercially available.
Embodiment
Embodiment 1
A kind of refrigerator sealing strip thermoplastic elastic material, by weight, including following components:
20 parts of SEBS；
30 parts of paraffin oil；
10 parts of polypropylene；
2 parts of the mixture of molecular sieve, silica and titanium dioxide；
Wherein, the SEBS (trade mark SEBS9551) buys Yu Lichang honor chemical industry.
Paraffin oil (model KF-550) purchase is in the auspicious vibration of South Korea.
The polypropylene is made of the polypropylene that melt flow rate (MFR) is respectively 6.5g/10min and 16g/10min, melt
Flow rate is respectively that polypropylene weight part of 6.5g/10min and 16g/10min is compared for 1:1.Melt flow rate (MFR) is 6.5g/
In Tai Su polypropylene Co., Ltd, melt flow rate (MFR) is poly- the third of 16g/10min for polypropylene (trade mark 5050) purchase of 10min
Alkene (SF203HMS) is bought in Co., Ltd, Borealis.
The mixture of the molecular sieve, silica and titanium dioxide is to first pass through caprylic acid modification, again load silver ion
Mixture.
The average grain diameter of the molecular sieve is 500nm, the average grain diameter of silica is 100nm, titanium dioxide is averaged
Partial size is 10nm.
The molecular sieve is Titanium Sieve Molecular Sieve.The Titanium Sieve Molecular Sieve purchase is in the limited public affairs of Nanjing Xian Feng nano material science and technology
Department.
The molecular sieve, silica, titanium dioxide weight percent are as follows: molecular sieve 40%, silica 30%,
Titanium dioxide 30%.
The mixture of the molecular sieve, silica and titanium dioxide first passes through that caprylic acid is modified, load silver ion again
Specific preparation step are as follows:
(1) molecular sieve, silica, titanium dioxide are added in 10g dehydrated alcohol, ultrasound；
(2) mixture in step (1) is heated to 80 DEG C, speed of agitator 400rpm is condensed back simultaneously.Then plus
Enter the dispersion liquid containing caprylic acid, contained caprylic acid is 0.1g, and after continuous heating 10h, centrifugation obtains the modified mixing of caprylic acid
Object；
(3) the modified mixture of the caprylic acid for taking 10g step (2) to obtain is added to the AgNO of 100mL 0.1mol/L3It is molten
In liquid, react 6h at 60 DEG C, filtering to get.
The preparation method of the thermoplastic elastic material, comprising the following steps:
S1 weighs raw material by above-mentioned parts by weight；
SEBS and paraffin oil are mixed 40min by S2 in blender, are then added polypropylene, molecular sieve, silica and
The mixture of titanium dioxide is mixed together 40min, obtains pre-composition；
S3 by pre-composition described in step S2 be placed in double screw extruder squeeze out, pelletizing to get.
Embodiment 2
A kind of refrigerator sealing strip thermoplastic elastic material, by weight, including following components:
45 parts of SEBS；
55 parts of paraffin oil；
40 parts of polypropylene；
15 parts of the mixture of molecular sieve, silica and titanium dioxide；
Wherein, the SEBS (trade mark SEBS9551) buys Yu Lichang honor chemical industry.
Paraffin oil (model KF-550) purchase is in the auspicious vibration of South Korea.
The polypropylene is made of the polypropylene that melt flow rate (MFR) is respectively 6.5g/10min and 16g/10min, melt
Flow rate is respectively that polypropylene weight part of 6.5g/10min and 16g/10min is compared for 1:1.Melt flow rate (MFR) is 6.5g/
In Tai Su polypropylene Co., Ltd, melt flow rate (MFR) is poly- the third of 16g/10min for polypropylene (trade mark 5050) purchase of 10min
Alkene (SF203HMS) is bought in Co., Ltd, Borealis.
The mixture of the molecular sieve, silica and titanium dioxide is to first pass through caprylic acid modification, again load silver ion
Mixture.
The average grain diameter of the molecular sieve is 500nm, the average grain diameter of silica is 100nm, titanium dioxide is averaged
Partial size is 10nm.
The molecular sieve is Titanium Sieve Molecular Sieve.The Titanium Sieve Molecular Sieve purchase is in the limited public affairs of Nanjing Xian Feng nano material science and technology
Department.
The molecular sieve, silica, titanium dioxide weight percent are as follows: molecular sieve 40%, silica 30%,
Titanium dioxide 30%.
The mixture of the molecular sieve, silica and titanium dioxide first passes through that caprylic acid is modified, load silver ion again
Specific preparation step are as follows:
(1) molecular sieve, silica, titanium dioxide are added in 75g dehydrated alcohol, ultrasound；
(2) mixture in step (1) is heated to 80 DEG C, speed of agitator 400rpm is condensed back simultaneously.Then plus
Enter the dispersion liquid containing caprylic acid, contained caprylic acid is 0.8g, and after continuous heating 20h, centrifugation obtains the modified mixing of caprylic acid
Object；
(3) the modified mixture of the caprylic acid for taking 10g step (2) to obtain is added to the AgNO of 100mL 0.1mol/L3It is molten
In liquid, react 6h at 60 DEG C, filtering to get.
The preparation method of the thermoplastic elastic material, comprising the following steps:
S1 weighs raw material by above-mentioned parts by weight；
SEBS and paraffin oil are mixed 60min by S2 in blender, are then added polypropylene, molecular sieve, silica and
The mixture of titanium dioxide is mixed together 60min, obtains pre-composition；
S3 by pre-composition described in step S2 be placed in double screw extruder squeeze out, pelletizing to get.
Embodiment 3
A kind of refrigerator sealing strip thermoplastic elastic material, by weight, including following components:
30 parts of SEBS；
40 parts of paraffin oil；
Polipropene 25 part；
10 parts of the mixture of molecular sieve, silica and titanium dioxide；
Wherein, the SEBS (trade mark SEBS9551) buys Yu Lichang honor chemical industry.
Paraffin oil (model KF-550) purchase is in the auspicious vibration of South Korea.
The polypropylene is made of the polypropylene that melt flow rate (MFR) is respectively 6.5g/10min and 16g/10min, melt
Flow rate is respectively that polypropylene weight part of 6.5g/10min and 16g/10min is compared for 1:1.Melt flow rate (MFR) is 6.5g/
In Tai Su polypropylene Co., Ltd, melt flow rate (MFR) is poly- the third of 16g/10min for polypropylene (trade mark 5050) purchase of 10min
Alkene (SF203HMS) is bought in Co., Ltd, Borealis.
The mixture of the molecular sieve, silica and titanium dioxide is to first pass through caprylic acid modification, again load silver ion
Mixture.
The average grain diameter of the molecular sieve is 500nm, the average grain diameter of silica is 100nm, titanium dioxide is averaged
Partial size is 10nm.
The molecular sieve is Titanium Sieve Molecular Sieve.The Titanium Sieve Molecular Sieve purchase is in the limited public affairs of Nanjing Xian Feng nano material science and technology
Department.
The molecular sieve, silica, titanium dioxide weight percent are as follows: molecular sieve 40%, silica 30%,
Titanium dioxide 30%.
The mixture of the molecular sieve, silica and titanium dioxide first passes through that caprylic acid is modified, load silver ion again
Specific preparation step are as follows:
(1) molecular sieve, silica, titanium dioxide are added in 50g dehydrated alcohol, ultrasound；
(2) mixture in step (1) is heated to 80 DEG C, speed of agitator 400rpm is condensed back simultaneously.Then plus
Enter the dispersion liquid containing caprylic acid, contained caprylic acid is 0.5g, and after continuous heating 15h, centrifugation obtains the modified mixing of caprylic acid
Object；
(3) the modified mixture of the caprylic acid for taking 10g step (2) to obtain is added to the AgNO of 100mL 0.1mol/L3It is molten
In liquid, react 6h at 60 DEG C, filtering to get.
The preparation method of the thermoplastic elastic material, specific steps are the same as embodiment 2.
Embodiment 4
A kind of refrigerator sealing strip thermoplastic elastic material, concrete component and parts by weight are the same as embodiment 3.Difference exists
In the average grain diameter of the molecular sieve is 800nm, the average grain diameter of silica is 300nm, the average grain diameter of titanium dioxide is
50nm。
The preparation method of the thermoplastic elastic material, specific steps are the same as embodiment 2.
Embodiment 5
A kind of refrigerator sealing strip thermoplastic elastic material, concrete component and parts by weight are the same as embodiment 3.Difference exists
In the average grain diameter of the molecular sieve is 600nm, the average grain diameter of silica is 200nm, the average grain diameter of titanium dioxide is
30nm。
The preparation method of the thermoplastic elastic material, specific steps are the same as embodiment 2.
Embodiment 6
A kind of refrigerator sealing strip thermoplastic elastic material, concrete component and parts by weight are the same as embodiment 5.Difference exists
In, the molecular sieve, silica, titanium dioxide weight percent are as follows: molecular sieve 55%, silica 40%, titanium dioxide
Titanium 5%.
The preparation method of the thermoplastic elastic material, specific steps are the same as embodiment 2.
Embodiment 7
A kind of refrigerator sealing strip thermoplastic elastic material, concrete component and parts by weight are the same as embodiment 5.Difference exists
In, the molecular sieve, silica, titanium dioxide weight percent are as follows: molecular sieve 40%, silica 40%, titanium dioxide
Titanium 20%.
The preparation method of the thermoplastic elastic material, specific steps are the same as embodiment 2.
Embodiment 8
A kind of refrigerator sealing strip thermoplastic elastic material, concrete component and parts by weight are the same as embodiment 5.Difference exists
In, the molecular sieve, silica, titanium dioxide weight percent are as follows: molecular sieve 50%, silica 35%, titanium dioxide
Titanium 15%.
The preparation method of the thermoplastic elastic material, specific steps are the same as embodiment 2.
Embodiment 9
A kind of refrigerator sealing strip thermoplastic elastic material, concrete component and parts by weight are the same as embodiment 8.Difference exists
In the mixture of the molecular sieve, silica and titanium dioxide is to first pass through Palmiticacid modification, again load silver ion
Mixture.
The mixture of the molecular sieve, silica and titanium dioxide is first through Palmiticacid modification, again load silver ion
Specific preparation step with embodiment 3.
The preparation method of the thermoplastic elastic material, specific steps are the same as embodiment 2.
Embodiment 10
With embodiment 8, difference exists for a kind of refrigerator sealing strip thermoplastic elastic material, concrete component and parts by weight
In the mixture of the molecular sieve, silica and titanium dioxide is to first pass through dodecanoic acid modification, again load silver ion
Mixture.
The mixture of the molecular sieve, silica and titanium dioxide first pass through dodecanoic acid is modified, load silver again from
The specific preparation step of son is the same as embodiment 3.
The preparation method of the thermoplastic elastic material, specific steps are the same as embodiment 2.
Comparative example 1
With embodiment 10, difference exists for a kind of refrigerator sealing strip thermoplastic elastic material, concrete component and parts by weight
In the mixture of the molecular sieve, silica and titanium dioxide replaces with the mixture of silica and titanium dioxide.It is described
The weight percent of silica, titanium dioxide are as follows: silica 60%, titanium dioxide 40%.
The preparation method of the thermoplastic elastic material, specific steps are the same as embodiment 2.
Comparative example 2
With embodiment 10, difference exists for a kind of refrigerator sealing strip thermoplastic elastic material, concrete component and parts by weight
In the mixture of the molecular sieve, silica and titanium dioxide replaces with the mixture of molecular sieve and titanium dioxide.Described point
The weight percent of son sieve, titanium dioxide are as follows: molecular sieve 60%, titanium dioxide 40%.
The preparation method of the thermoplastic elastic material, specific steps are the same as embodiment 2.
Comparative example 3
With embodiment 10, difference exists for a kind of refrigerator sealing strip thermoplastic elastic material, concrete component and parts by weight
In the mixture of the molecular sieve, silica and titanium dioxide replaces with the mixture of molecular sieve and silica.Described point
The weight percent of son sieve, silica are as follows: molecular sieve 60%, titanium dioxide 40%.
The preparation method of the thermoplastic elastic material, specific steps are the same as embodiment 2.
Comparative example 4
With embodiment 10, difference exists for a kind of refrigerator sealing strip thermoplastic elastic material, concrete component and parts by weight
In the mixture of the molecular sieve, silica and titanium dioxide is without the mixed of fatty acid modified, direct load silver ion
Close object.
The specific preparation step of the mixture load silver ion of the molecular sieve, silica and titanium dioxide are as follows:
(1) molecular sieve, silica, titanium dioxide are added in 50g dehydrated alcohol, ultrasound；
(2) AgNO of 100mL 0.1mol/L is added in the mixture that step (2) obtains3Solution reacts at 60 DEG C
6h, filtering to get.
The preparation method of the thermoplastic elastic material, specific steps are the same as embodiment 2.
Comparative example 5
With embodiment 10, difference exists for a kind of refrigerator sealing strip thermoplastic elastic material, concrete component and parts by weight
In the mixture of the molecular sieve, silica and titanium dioxide replaces with molecular sieve, silica and titanium dioxide and passes through respectively
Cross that dodecanoic acid is modified, load silver ion is mixed to prepare again.
The modified molecular sieve preparation step of the dodecanoic acid of the load silver ion are as follows:
(1) 5g molecular sieve is added in 25g dehydrated alcohol, ultrasound；
(2) mixture in step (1) is heated to 80 DEG C, speed of agitator 400rpm is condensed back simultaneously.Then plus
Enter the dispersion liquid containing dodecanoic acid, contained dodecanoic acid is 0.25g, and after continuous heating 15h, centrifugation obtains n-dodecane
The modified molecular sieve of acid；
(3) the modified molecular sieve of the dodecanoic acid for taking 10g step (2) to obtain, is added to 50mL 0.1mol/L's
AgNO3In solution, react 6h at 60 DEG C, filtering to get.
The modified silica preparation step of the dodecanoic acid of the load silver ion are as follows:
(1) 3.5g silica is added in 20g dehydrated alcohol, ultrasound；
(2) mixture in step (1) is heated to 80 DEG C, speed of agitator 400rpm is condensed back simultaneously.Then plus
Enter the dispersion liquid containing dodecanoic acid, contained dodecanoic acid is 0.18g, and after continuous heating 15h, centrifugation obtains n-dodecane
The modified silica of acid；
(3) the modified silica of the dodecanoic acid for taking 10g step (2) to obtain, is added to 40mL 0.1mol/L's
AgNO3In solution, react 6h at 60 DEG C, filtering to get.
The modified titanium dioxide preparation step of the dodecanoic acid of the load silver ion are as follows:
(1) 1.5g titanium dioxide is added in 8g dehydrated alcohol, ultrasound；
(2) mixture in step (1) is heated to 80 DEG C, speed of agitator 400rpm is condensed back simultaneously.Then plus
Enter the dispersion liquid containing dodecanoic acid, contained dodecanoic acid is 0.07g, and after continuous heating 15h, centrifugation obtains n-dodecane
The modified titanium dioxide of acid；
(3) the modified titanium dioxide of the dodecanoic acid for taking 10g step (2) to obtain, is added to 10mL 0.1mol/L's
AgNO3In solution, react 6h at 60 DEG C, filtering to get.
By the modified molecular sieve of the dodecanoic acid of load silver ion obtained above, the dodecanoic acid of load silver ion
The modified titanium dioxide mixing of the dodecanoic acid of modified titanium dioxide, load silver ion.
The preparation method of the thermoplastic elastic material, specific steps are the same as embodiment 2.
Comparative example 6
With embodiment 10, difference exists for a kind of refrigerator sealing strip thermoplastic elastic material, concrete component and parts by weight
In, the mixture of the molecular sieve, silica and titanium dioxide is first load silver ion, modified using dodecanoic acid
Mixture.
The mixture elder generation load silver ion of the molecular sieve, silica and titanium dioxide, changes using dodecanoic acid
The preparation step of property are as follows:
(1) molecular sieve, silica, titanium dioxide are added in 50g dehydrated alcohol, ultrasound；100mL 0.1mol/ is added
The AgNO of L3Solution reacts 6h at 60 DEG C, filtering.
(2) mixture in step (1) is heated to 80 DEG C, speed of agitator 400rpm, while is condensed back and then adds
Enter the dispersion liquid containing positive lauric acid/dodecanoic acid, contained dodecanoic acid is 0.5g, after continuous heating 15h, centrifugation to get.
The preparation method of the thermoplastic elastic material, specific steps are the same as embodiment 2.
Performance test
The thermoplastic elastic material prepared to above-described embodiment and comparative example is tested for the property.
Shore hardness (A): it is tested with reference to ASTM D-2240.
Tensile strength (MPa), elongation at break (%): it is tested with reference to ASTM D-412.
Anti-mildew denaturation: thermoplastic elastic material is placed in climatic chamber, and temperature is 30 ± 2 DEG C, humidity 95%
More than.Eight kinds of moulds (aspergillus niger, discoloration aspergillus, Chaetomium globosum, Huang Qusu, trichoderma, withered mould, Paecilomyces varioti, bud branch are mould) are mixed
Conjunction is sprayed on specimen surface, then places in experimental box, and once, the obvious mildew of nothing is then conjunction after 840 hours for observation in every 168 hours
Lattice.
Feel: test crowd is divided into 16 groups, every group of 5 people carry out sensory evaluation to thermoplastic elastic material respectively.It comments
Dividing sensory effects total score in table is 5 points；5 points are best results, indicate very fine and smooth, good hand touch；4 points are preferably, to indicate relatively thin
It is greasy, good hand touch；3 points are exquisitenesses, and feel is general；3 points the following are unacceptable ranges.
Thermoplastic elastic material the performance test results
The above described is only a preferred embodiment of the present invention, be not the limitation for making other forms to invention, it is any
Those skilled in the art are changed or are changed to the equivalent of equivalent variations possibly also with the technology contents of the disclosure above
Embodiment, but without departing from the technical solutions of the present invention, above embodiments are made according to the technical essence of the invention
Any simple modification, equivalent variations and remodeling, still fall within the protection scope of technical solution of the present invention.
Claims (10)
1. a kind of refrigerator sealing strip thermoplastic elastic material, which is characterized in that by weight, including following components:
20~45 parts of SEBS；
30~55 parts of paraffin oil；
10~40 parts of polypropylene；
2~15 parts of the mixture of molecular sieve, silica and titanium dioxide；
Wherein, the mixture of the molecular sieve, silica and titanium dioxide is to first pass through fatty acid modified, load silver ion again
Mixture.
2. thermoplastic elastic material as described in claim 1, which is characterized in that the shore hardness of the SEBS be 50~
80A。
3. thermoplastic elastic material as described in claim 1, which is characterized in that the dynamic viscosity of the paraffin oil be 80~
200mm2/s。
4. thermoplastic elastic material as described in claim 1, which is characterized in that the polypropylene is by melt flow rate (MFR) point
Not Wei 5~20g/10min one or more polypropylene composition.
5. thermoplastic elastic material as claimed in claim 4, which is characterized in that the polypropylene is by melt flow rate (MFR) point
Not Wei 5~10g/10min and 11~20g/10min polypropylene composition.
6. thermoplastic elastic material as described in claim 1, which is characterized in that the average grain diameter of the molecular sieve is 500
~800nm, silica average grain diameter be 100~300nm, the average grain diameter of titanium dioxide is 10~50nm.
7. thermoplastic elastic material as claimed in claim 6, which is characterized in that the molecular sieve, silica and dioxy
Change the weight percent of molecular sieve, silica, titanium dioxide in the mixture of titanium are as follows:
Molecular sieve 40~55%；
Silica 30~40%；
Titanium dioxide remainder amount.
8. thermoplastic elastic material as claimed in claim 7, which is characterized in that the molecular sieve, silica and dioxy
The mixture for changing titanium is fatty acid modified, load silver ion again the mixture for first passing through carbon atom number and being 8~16.
9. thermoplastic elastic material as claimed in claim 8, which is characterized in that the molecular sieve, silica and dioxy
The mixture for changing titanium is fatty acid modified, load silver ion again the mixture for first passing through carbon atom number and being 8~12.
10. a kind of preparation method of thermoplastic elastic material as described in any one of claims 1 to 9, which is characterized in that packet
Include following steps:
S1 weighs raw material by above-mentioned parts by weight；
SEBS and paraffin oil are mixed 40~60min by S2 in blender, are then added polypropylene, molecular sieve, silica and
The mixture of titanium dioxide is mixed together 40~60min, obtains pre-composition；
S3 by pre-composition described in step S2 be placed in double screw extruder squeeze out, pelletizing to get.
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