CN106633335B - A kind of degradable foaming sole and preparation method thereof containing polycarbonate alloy - Google Patents
A kind of degradable foaming sole and preparation method thereof containing polycarbonate alloy Download PDFInfo
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
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- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/04—Plastics, rubber or vulcanised fibre
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2469/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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- 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
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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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
- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
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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
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- 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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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C08L2312/00—Crosslinking
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Abstract
The invention belongs to organic high molecular compound technical fields, a kind of degradable foaming sole and preparation method thereof containing polycarbonate alloy is provided, the degradable foaming sole containing polycarbonate alloy is on the basis of guaranteeing has the good combination properties such as light, wear-resisting, on-slip, dimensionally stable, has biodegradability, white pollution bring environmental problem can be alleviated, meet the developing direction of current material；The degradable foaming sole containing polycarbonate alloy is by EVA, the thermoplastic elastomer material containing polycarbonate alloy, low melting point polyester chip, foaming agent, crosslinking agent B IBP, cross-linking aid, zinc stearate, stearic acid, anti-wear agent, corn flour, nanometer calcium carbonate, it is obtained by mixing, mill, granulation, then through an ejection formation.
Description
Technical field
The invention belongs to organic high molecular compound technical fields, in particular to a kind of containing the degradable of polycarbonate alloy
Foamed shoe sole and preparation method thereof.
Background technique
There is the features such as skidding, puncture-resistant and low temperature are not hardened in EVA foamed material.Elastomer and EVA compatibility are fine, easily
Dispersed phase is formed in system, can reduce the active force between strand, plays plasticization, the addition of elastomeric material,
The performances such as compressive deformation, wear-resisting, the anti-skidding, folding of EVA foamed material can be improved, cheap, the more superior material of performance is made
Material, to meet special requirement of the people to material property.Meanwhile density, the tearing strength of EVA foamed material are basically unchanged, and are drawn
It is on a declining curve to stretch intensity, hardness, elongation at break increases, and material softness improves.
Application No. is 2014103285718 patents to disclose a kind of preparation side of rubber plastic foam material containing polycarbonate
Method, material of main part are EVA70 parts and 20-40 parts of styrene type elastomeric material containing polycarbonate, obtain density lower than 0.4
g/cm3, DIN is wear-resisting is lower than 100 mm3, wet type on-slip coefficient be higher than 0.6 rubber plastic foam material, have it is light, high-elastic, high
The features such as on-slip, high-dimensional stability, and have excellent tensile strength and tear strength, be particularly suitable for all kinds of shoes accessories,
The application of sole material etc., comfort is good, long service life.But 175 DEG C of the mold temperature of its ejection formation-
185 DEG C, the time is -270 seconds 250 seconds, and production efficiency is obviously relatively low, and vulcanization time need further to shorten, and use
For bridging agent cumyl peroxide (DCP) there are obvious stink, the summation containing acetophenone and 2- phenyl -2- propyl alcohol is more than 500mg/
Kg does not meet the environmental requirement of " Detox action "；Use the hair of bridging agent two-(t-butylperoxyisopropyl) benzene (BIBP)
Steep summation of the sole containing acetophenone and 2- phenyl -2- propyl alcohol be more than 40mg/kg, be hopeful to meet main international top-brand manufacturer include
The limitation of Nike, Adidas, Si Kaiqi etc. require (summation of acetophenone and 2- phenyl -2- propyl alcohol is lower than 50mg/kg), but
The phenomenon that leading to sticking to mould there are free radical residual.So the cross-linking system of foamed shoe sole becomes industry technology personnel and closes the most
One of theme of note and one of problem in the urgent need to address.
Summary of the invention
Therefore, for above-mentioned problem, the present invention propose a kind of degradable foaming sole containing polycarbonate alloy and its
Preparation method, the degradable foaming sole containing polycarbonate alloy are guaranteeing there is light, wear-resisting, on-slip, dimensionally stable
On the basis of equal good combination properties, has biodegradability, white pollution bring environmental problem can be alleviated, meet current material
The developing direction of material, and the preparation method of the degradable foaming sole containing polycarbonate alloy is easy to operate, Yi Shixian,
It is suitble to quantitatively manufacture and uses.
To realize the above-mentioned technical purpose, the solution that the present invention takes are as follows: a kind of containing the degradable of polycarbonate alloy
Foamed shoe sole, which is characterized in that including following component:
50 parts of EVA
30-40 parts of thermoplastic elastomer material containing polycarbonate alloy
10-15 parts of low melting point polyester chip
1.8-2.2 parts of foaming agent
0.7-1.2 parts of crosslinking agent B IBP
0.1-0.4 parts of cross-linking aid
0.6-1.0 parts of zinc stearate
0.6-1.0 parts of stearic acid
1-2 parts of anti-wear agent
8-12 parts of corn flour
5 parts of nanometer calcium carbonate；
Wherein the thermoplastic elastomer material containing polycarbonate alloy includes following component: styrene-butadiene-
50 parts of styrene block copolymer (SBS), 40 parts of degradable polycarbonate alloy, 4 parts of compatilizer, 0.8 part of zinc stearate, photo-thermal
0.4 part and 10 parts of vegetable oil of stabilizer.
Further, the degradable polycarbonate alloy includes at least polycarbonate/polylactic acid alloy, (PC/PLA is closed
Gold), polycarbonate/polybutylene succinate (PBS) alloy (PC/PBS alloy), polycarbonate/polycaprolactone alloy (PC/PCL close
One of gold);The mass ratio of polycarbonate in the degradable polycarbonate alloy is 20-50%.
Further, it is aliphatic PC, aromatic series PC, rouge that the PC in the degradable polycarbonate alloy, which is included at least,
One of fat race-aromatic series PC.
Further, the Styrene-Butadiene-Styrene Block Copolymer (SBS) is factice, oil-containing mass ratio
30%-35%。
Further, the compatilizer includes at least Maleic anhydride-containg polyethylene (SBS-g-MAH), methyl methacrylate
Ester is grafted one of SBS (SBS-g-MMA), ethylene-octene copolymer grafted maleic anhydride (POE-g-MAH).
Further, optothermal stabilizer includes at least dilauryl thiodipropionate, diphenyl phosphite, phosphorous acid three
One of phenyl ester, hindered phenol, hydroxybenzotriazole, cinnamate these compounds.
Further, component proportion is as follows:
50 parts of EVA
35 parts of thermoplastic elastomer material containing polycarbonate alloy
12 parts of low melting point polyester chip
2.0 parts of foaming agent
0.9 part of crosslinking agent B IBP
0.4 part of cross-linking aid
0.8 part of zinc stearate
0.6 part of stearic acid
1 part of anti-wear agent
10 parts of corn flour
5 parts of nanometer calcium carbonate.
Further, the micro melting point of the low melting point polyester chip is 75 DEG C -115 DEG C.
Further, the cross-linking aid is N, N- dihydroxy ethyl-open-chain crown ether.
A kind of preparation method of the degradable foaming sole containing polycarbonate alloy, includes the following steps:
Step 1, thermoplastic elastomer material of the preparation containing polycarbonate alloy: s-B-S is embedding
Section copolymer (SBS), degradable polycarbonate alloy, compatilizer, zinc stearate, optothermal stabilizer and vegetable oil, it is mixed in high speed
It is premixed in clutch 5-8 minutes, then by premix by double screw extruder, melting extrusion, cooling are made at 130 DEG C -140 DEG C
Grain, obtains the thermoplastic elastomer material containing polycarbonate alloy；
Step 2, degradable material rice of the preparation containing polycarbonate alloy: by EVA, containing the thermoplasticity of polycarbonate alloy
Elastomeric material, low melting point polyester chip, zinc stearate, stearic acid, anti-wear agent, corn flour, nanometer calcium carbonate mixing progress are close
Refining, adjustment smelting temperature control is 90 DEG C -95 DEG C, is kept for 4-6 minutes, crosslinking agent B IBP, cross-linking aid and hair is then added
Infusion continues mixing heating, and drop temperature is 100 DEG C -103 DEG C, then carries out mill, is granulated, and obtains containing polycarbonate alloy
Degradable material rice；
Step 3: the degradable material rice containing polycarbonate alloy being added in the hopper that EVA projects board, once penetrated
It forms out, penetrates 90 DEG C -105 DEG C of rifle temperature, mold temperature is 175 DEG C -180 DEG C, and the time is -200 seconds 180 seconds, obtains described contain
The degradable foaming sole of polycarbonate alloy.
Wherein, the VA content mass ratio 14%-30% range of EVA described in step 2, preferably VA content mass ratio 18%-26%
Range.
Wherein, foaming agent described in step 2 is azodicarbonamide (AC).
Wherein, zinc stearate described in step 2 is the zinc stearate of direct method production.
Wherein, stearic acid described in step 2 is stearic acid 1801.
Wherein, anti-wear agent described in step 2 be Chengdu think it is vertical can Science and Technology Ltd. NM-2.
Further, an ejection formation in step 3, penetrate one section of rifle, two sections, three sections of temperature be 90 DEG C, 95 respectively
DEG C, 100 DEG C, mold temperature is preferably 175 DEG C -176 DEG C, and the time is preferably -190 seconds 185 seconds.
By taking preceding solution, the invention has the following beneficial effects:
1, the present patent application is by adding cross-linking aid N, the N- dihydroxy ethyl-of 52 DEG C of fusing point, 338 DEG C of boiling point to methylbenzene
Amine forms organic oxidation reduction system with crosslinking agent B IBP, can form arylamine alkyl diradical in cross-linking process, accelerate free radical
Cause polymer crosslinking, that is, improve cross-linked speed TC90, reduce crosslinking temperature, shorten an ejection formation when
Between, production efficiency is improved, can be saved time and human cost；Simultaneously as cross-linking aid introduces, the decomposition of BIBP is reduced
Temperature, such as when cross-linking aid addition parts by weight are 0.2 part and 0.4 part, the decomposition temperature of BIBP reduces by 6.5 DEG C, 10.3 respectively
DEG C (as shown in Fig. 1), makes the fully reacting in cross-linking process of the free radical in system, avoids viscous caused by free radical residual
Mould phenomenon, preparation method according to the invention are produced as a trial for continuous 10 days, and sole stripping result is preferable, does not find mold sticking, shoes
The fine pattern at bottom is still clear；Foamed shoe sole produced by the present invention, through GCMS detection containing acetophenone and 2- phenyl -2- propyl alcohol
Summation is 36mg/kg (embodiment 1), meets the environmental requirement of main international top-brand manufacturer at present.
2, the present patent application uses degradable polycarbonate alloy PC/PLA alloy, PC/PBS alloy and/or PC/PCL
Alloy does not improve the dimensionally stable of foamed material, the performances such as wear-resisting merely with polycarbonate, and due to PLA, PBS and PCL
All there is preferable biological degradability, easily decomposed by the multiple-microorganism of nature or the intracorporal enzyme of animals and plants, metabolism, final point
Solution is carbon dioxide and water, is typical fully biodegradable polymer material, and the present invention is in conjunction with using vegetable oil, corn
Starch, the foamed shoe sole obtained containing polycarbonate alloy can Partial digestion, residue also exists with the powder little particle of dispersion,
Alleviate white pollution bring environmental problem significantly, saves petroleum resources and reduce global greenhouse effect simultaneously, meet current material
Developing direction.
3, the present patent application increases sole material using having the characteristics that fusing point is low, low-melting point polyester of good fluidity
Polarity, enhance the interaction force of sole surface and water, effectively increase the wet-sliding resistant performance of sole；Low-melting point polyester
Glass transition temperature is higher than 55 DEG C, can effectively improve the dimensional stability at EVA shoe bottom；Low-melting point polyester is a kind of and most of
Fibre-forming polymer has the polymer of excellent compatibility, so that having according to sole made from the present patent application and vamp good
Coating performance, especially EVA shoe bottom are directly fitted with flying to knit vamp, significantly improve the peel strength of sole and vamp.
Detailed description of the invention
Fig. 1 is the curve graph that cross-linking aid content influences crosslinking agent B IBP decomposition temperature.
Test condition: the DSC Q2000 of U.S.'s TA instrument, 0 DEG C -210 DEG C of Range of measuring temp, 10 DEG C/minute of heating rate
Clock, 3.1 mg -4.3mg of sample size.
Spectrogram explanation: curve 1 is BIBP and N, and N- dihydroxy ethyl-open-chain crown ether mass ratio is 1:0.4；Curve 2 is
The mass ratio of BIBP and N, N- dihydroxy ethyl-open-chain crown ether is 1:0.2；Curve 3 is BIBP.The melting temperature of curve 1,2,3
Respectively 49.05 DEG C, 49.15 DEG C, 48.53 DEG C, decomposition temperature are respectively 169.48 DEG C, 173.31 DEG C, 179.81 DEG C, are shown
N is added, N- dihydroxy ethyl-open-chain crown ether significantly reduces the decomposition temperature of BIBP, and has substantially no effect on the melting temperature of BIBP
Degree.
Specific embodiment
Now in conjunction with specific embodiment, the present invention is further described.
Embodiment 1:
A kind of preparation method of the degradable foaming sole containing polycarbonate alloy, includes the following steps:
Step 1, thermoplastic elastomer material of the preparation containing polycarbonate alloy: by SBS F875 50 by weight
Part, 40 parts of degradable polycarbonate alloy PC/PLA alloy (PC content mass ratio 45%), compatilizer Maleic anhydride-containg polyethylene 4
Part, 0.8 part of zinc stearate, 0.4 part of antioxidant B1004 and 10 parts of vegetable oil premix 7 minutes in super mixer, then will
Premix is by double screw extruder, melting extrusion, cooling granulation at 135 DEG C, and it is plastic to obtain the heat containing polycarbonate alloy
Property elastomeric material；
Step 2, preparation the degradable material rice containing polycarbonate alloy: the degradable material rice containing polycarbonate alloy by
The component of following parts by weight is prepared:
20 parts of EVA 7350M
30 parts of EVA 7470M
35 parts of thermoplastic elastomer material containing polycarbonate alloy
12 parts of low melting point polyester chip (105 DEG C of fusing point)
2.0 parts of blowing agent AC
0.9 part of crosslinking agent B IBP
0.4 part of dihydroxy ethyl-open-chain crown ether of cross-linking aid N, N-
0.8 part of zinc stearate (production of Ling Huxinwang chemical company)
1,801 0.6 parts of stearic acid
1 part of anti-wear agent NM-2
10 parts of corn flour
5 parts of nanometer calcium carbonate
First other raw materials other than crosslinking agent B IBP, cross-linking aid and foaming agent are mixed and carry out mixing, adjustment
Smelting temperature control is 93 DEG C -95 DEG C, is kept for 5 minutes, crosslinking agent B IBP, cross-linking aid and foaming agent is then added, continued
Mixing heating, drop temperature are 101 DEG C, then carry out mill, are granulated, and obtain the degradable material rice containing polycarbonate alloy；
Degradable material rice containing polycarbonate alloy is added in the hopper that EVA projects board by step 3, is once penetrated
Form out, penetrate one section of rifle, two sections, three sections of temperature be 90 DEG C, 95 DEG C, 100 DEG C respectively, mold temperature is 176 DEG C, and the time is
190 seconds, obtain the degradable foaming sole containing polycarbonate alloy.
The above-mentioned degradable foaming sole containing polycarbonate alloy being prepared, Tc90 be 3 points 22 seconds, density 0.23
g/cm3, hardness 55, the wear-resisting 167cm of DIN3, dimensional contraction 0.5%, rebound degree 53%, 0.85 wet type of on-slip coefficient (smooth) dry type
0.60, acetophenone content 19mg/kg, 2- phenyl -2- alcohol content 17mg/kg.
Embodiment 2:
The preparation method of the degradable foaming sole containing polycarbonate alloy of embodiment 2 substantially with the system in embodiment 1
Preparation Method is identical, except that:
In step 1: polycarbonate alloy is PC/PBS alloy (PC content mass ratio 35%), compatilizer is base acrylic acid
Methyl esters is grafted SBS (SBS-g-MMA).
In step 2: 50 parts of EVA 7470M, 10 parts, 8 parts of corn flour of low melting point polyester chip (85 DEG C of fusing point).
In step 3: 175 DEG C of mold temperature, the time 180 seconds.
The above-mentioned degradable foaming sole containing polycarbonate alloy being prepared, Tc90 be 3 points 12 seconds, density 0.22
g/cm3, hardness 54, the wear-resisting 189cm of DIN3, dimensional contraction 1.0%, rebound degree 56%, 0.73 wet type of on-slip coefficient (smooth) dry type
0.51, acetophenone content 16mg/kg, 2- phenyl -2- alcohol content 16mg/kg.
Embodiment 3:
The preparation method of the degradable foaming sole containing polycarbonate alloy of embodiment 3 substantially with the system in embodiment 1
Preparation Method is identical, except that:
In step 1: polycarbonate alloy is PC/PLA alloy (PC content mass ratio 20%).
In step 2: 50 parts of EVA V5110J, 40 parts of thermoplastic elastomer material, eutectic containing polycarbonate alloy
Point 15 parts of polyester slice (115 DEG C of fusing point), cross-linking aid N, N- dihydroxy ethyl -0.3 part of open-chain crown ether, 2 parts of anti-wear agent, jade
12 parts of rice flour.
In step 3: 178 DEG C of mold temperature, the time 190 seconds.
The above-mentioned degradable foaming sole containing polycarbonate alloy being prepared, Tc90 be 3 points 28 seconds, density 0.22
g/cm3, hardness 55, the wear-resisting 234cm of DIN3, dimensional contraction 1.3%, rebound degree 50%, 0.84 wet type of on-slip coefficient (smooth) dry type
0.63, acetophenone content 15mg/kg, 2- phenyl -2- alcohol content 22mg/kg.
Embodiment 4:
The preparation method of the degradable foaming sole containing polycarbonate alloy of embodiment 4 substantially with the system in embodiment 1
Preparation Method is identical, except that:
In step 1: polycarbonate alloy is PC/PCL alloy (PC content mass ratio 50%), compatilizer is ethylene-octene
Copolymer grafted maleic anhydride (POE-g-MAH).
In step 2: 15 parts of EVA 7470M, 35 parts of EVA 7350M, the thermoplastic elastomer containing polycarbonate alloy
30 parts of body material, 12 parts of low melting point polyester chip (95 DEG C of fusing point), cross-linking aid N, N- dihydroxy ethyl-open-chain crown ether 0.1
Part.
In step 3: 180 DEG C of mold temperature, the time 200 seconds.
The above-mentioned degradable foaming sole containing polycarbonate alloy being prepared, Tc90 be 3 points 35 seconds, density 0.23
g/cm3, hardness 56, the wear-resisting 158cm of DIN3, dimensional contraction 0.6%, rebound degree 51%, 0.69 wet type of on-slip coefficient (smooth) dry type
0.49, acetophenone content 15mg/kg, 2- phenyl -2- alcohol content 14mg/kg.
Comparative example 1:
The preparation method of the degradable foaming sole containing polycarbonate alloy of comparative example 1 and the preparation side in embodiment 1
Method is identical, except that:
In step 2: 0 part of cross-linking aid.
In step 3: 185 DEG C of mold temperature, the time 240 seconds.
The above-mentioned degradable foaming sole containing polycarbonate alloy being prepared, Tc90 be 4 points 10 seconds, density 0.23
g/cm3, hardness 55, the wear-resisting 175cm of DIN3, dimensional contraction 0.6%, rebound degree 52%, 0.85 wet type of on-slip coefficient (smooth) dry type
0.59, acetophenone content 29mg/kg, 2- phenyl -2- alcohol content 12mg/kg.
After the data preparation of above-described embodiment 1~4 and comparative example 1, obtain such as following table 1(note: Tc90 is using foaming vulcanization
6 minutes time of 180 DEG C of instrument UR-2030SD test temperature, hardness are tested using GS-701N hardometer, and DIN is wear-resisting according to GB/T
9867:2001 test, dimensional contraction rate are tested for 4 hours according to 50 degree, and rebound degree test uses GT-7042-RE type impact elasticity
Testing machine, tearing strength test right-angle tearing according to GB/T 529-2008, and tensile strength is tested according to GB/T 528-2009, only
Sliding coefficient is tested according to TM144:2011, and acetophenone content and 2- phenyl -2- alcohol content are that sole room temperature opens wide placement 5 days
GCMS test analysis (detection limit 2mg/kg) is recycled by acetone extract):
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | |
| Tc90 (point: the second) | 3:22 | 3:12 | 3:28 | 3:35 | 4:10 |
| Density (g/cm3) | 0.23 | 0.22 | 0.22 | 0.23 | 0.23 |
| Hardness | 55 | 54 | 55 | 56 | 55 |
| Wear-resisting (the mm of DIN3) | 167 | 189 | 234 | 158 | 175 |
| Dimensional contraction rate (%) | 0.5 | 1.0 | 1.3 | 0.6 | 0.6 |
| Resilience (%) | 53 | 56 | 50 | 51 | 52 |
| On-slip coefficient (smooth dry type) | 0.85 | 0.73 | 0.84 | 0.69 | 0.85 |
| On-slip coefficient (smooth wet type) | 0.60 | 0.51 | 0.63 | 0.49 | 0.59 |
| Acetophenone content (mg/kg) | 19 | 16 | 15 | 15 | 29 |
| 2- phenyl -2- alcohol content (mg/kg) | 17 | 16 | 22 | 14 | 12 |
Table 1: the performance parameter table of comparisons of degradable foaming sole prepared by Examples 1 to 4 and comparative example 1.
In conclusion guaranteeing that there is matter according to the degradable foaming sole produced by the present invention containing polycarbonate alloy
Gently, on the basis of the good combination properties such as wear-resisting, on-slip, dimensionally stable, have biodegradability, white pollution can be alleviated and brought
Environmental problem, meet the developing direction of current material, be particularly suitable for the application of all kinds of shoes accessories, sole material etc., relax
Adaptive is good, is suitble to industrialized production.
The foregoing descriptions are merely the embodiment using this origination techniques content, any those skilled in the art use this wound
Make done modifications and changes, all belong to the scope of the patents of this creation opinion, and is not limited to those disclosed embodiments.
Claims (6)
1. a kind of degradable foaming sole containing polycarbonate alloy, which is characterized in that including following component:
50 parts of EVA
30-40 parts of thermoplastic elastomer material containing polycarbonate alloy
10-15 parts of low melting point polyester chip
1.8-2.2 parts of foaming agent
0.7-1.2 parts of crosslinking agent B IBP
0.1-0.4 parts of cross-linking aid
0.6-1.0 parts of zinc stearate
0.6-1.0 parts of stearic acid
1-2 parts of anti-wear agent
8-12 parts of corn flour
5 parts of nanometer calcium carbonate；
Wherein the thermoplastic elastomer material containing polycarbonate alloy includes following component: styrene-butadiene-benzene second
50 parts of alkene block copolymer (SBS), 40 parts of degradable polycarbonate alloy, 4 parts of compatilizer, 0.8 part of zinc stearate, photo-thermal are stablized
0.4 part and 10 parts of vegetable oil of agent；
The Styrene-Butadiene-Styrene Block Copolymer (SBS) is factice, oil-containing mass ratio 30%-35%；
The degradable polycarbonate alloy includes at least polycarbonate/polylactic acid alloy (PC/PLA alloy), polycarbonate/poly-
One of succinic acid-butanediol ester alloy (PC/PBS alloy), polycarbonate/polycaprolactone alloy (PC/PCL alloy);Institute
The mass ratio for stating the polycarbonate in degradable polycarbonate alloy is 20-50%；
The cross-linking aid is N, N- dihydroxy ethyl open-chain crown ether.
2. the degradable foaming sole according to claim 1 containing polycarbonate alloy, it is characterised in that: described degradable
It is one of aliphatic PC, aromatic series PC, aliphatic-aromatic PC that PC in polycarbonate alloy, which is included at least,.
3. the degradable foaming sole according to claim 1 containing polycarbonate alloy, it is characterised in that: described compatible
Agent includes at least Maleic anhydride-containg polyethylene (SBS-g-MAH), methyl methacrylate-grafted SBS (SBS-g-MMA), ethylene-
One of octene copolymer grafted maleic anhydride (POE-g-MAH).
4. the degradable foaming sole according to claim 1 containing polycarbonate alloy, which is characterized in that including as follows
Component:
50 parts of EVA
35 parts of thermoplastic elastomer material containing polycarbonate alloy
12 parts of low melting point polyester chip
2.0 parts of foaming agent
0.9 part of crosslinking agent B IBP
0.4 part of cross-linking aid
0.8 part of zinc stearate
0.6 part of stearic acid
1 part of anti-wear agent
10 parts of corn flour
5 parts of nanometer calcium carbonate.
5. the degradable foaming sole according to claim 1 containing polycarbonate alloy, it is characterized in that being: the eutectic
The micro melting point of point polyester slice is 75 DEG C -115 DEG C.
6. a kind of preparation method of any degradable foaming sole containing polycarbonate alloy of claim 1-5, special
Sign is, includes the following steps:
Step 1, thermoplastic elastomer material of the preparation containing polycarbonate alloy: s-B-S block is total to
Polymers (SBS), degradable polycarbonate alloy, compatilizer, zinc stearate, optothermal stabilizer and vegetable oil, in super mixer
Middle premix 5-8 minutes, then by premix by double screw extruder, melting extrusion, cooling granulation at 130 DEG C -140 DEG C,
Obtain the thermoplastic elastomer material containing polycarbonate alloy；
Step 2, degradable material rice of the preparation containing polycarbonate alloy: by EVA, containing the thermoplastic elastomer of polycarbonate alloy
Body material, low melting point polyester chip, zinc stearate, stearic acid, anti-wear agent, corn flour, nanometer calcium carbonate mixing carry out mixing, adjust
Whole smelting temperature control is 90 DEG C -95 DEG C, is kept for 4-6 minutes, crosslinking agent B IBP, cross-linking aid and foaming agent is then added,
Continue mixing heating, drop temperature is 100 DEG C -103 DEG C, then carries out mill, is granulated, and is obtained containing the degradable of polycarbonate alloy
Expect rice；
Step 3: the degradable material rice containing polycarbonate alloy being added in the hopper that EVA projects board, once projected into
Type penetrates 90 DEG C -105 DEG C of rifle temperature, and mold temperature is 175 DEG C -180 DEG C, and the time is -200 seconds 180 seconds, obtains described containing poly- carbon
The degradable foaming sole of acid esters alloy.
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| CN108586910A (en) * | 2018-05-16 | 2018-09-28 | 莆田市百合鞋业有限公司 | A kind of skateboard sole and its manufacture craft |
| CN109749220A (en) * | 2019-01-11 | 2019-05-14 | 石狮市中纺学服装及配饰产业研究院 | A kind of degradable shoes materials of novel pla-pcl and preparation method |
| CN110885487A (en) * | 2019-10-28 | 2020-03-17 | 茂泰(福建)鞋材有限公司 | Preparation method of biodegradable foamed sole |
| CN110885486A (en) * | 2019-10-28 | 2020-03-17 | 茂泰(福建)鞋材有限公司 | Method for manufacturing foamed sole |
| CN111227427A (en) * | 2020-01-16 | 2020-06-05 | 浙江荣威鞋业有限公司 | Shoe with antibacterial sole and preparation process thereof |
| CN111205546A (en) * | 2020-02-14 | 2020-05-29 | 华侨大学 | Preparation method of EVA/TPU/PBS blended foamed shoe material |
| CN111440423B (en) * | 2020-05-20 | 2021-10-15 | 安踏（中国）有限公司 | Biodegradable foamed shoe midsole material and preparation method thereof |
| CN112157861B (en) * | 2020-08-27 | 2022-11-08 | 茂泰(福建)鞋材有限公司 | Preparation method of secondary mould pressing foaming sole |
| CN114434718A (en) * | 2022-01-23 | 2022-05-06 | 浙江奥康鞋业股份有限公司 | Novel physical two-color double-density foamed sole process and shoes made by same |
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| CN102653627A (en) * | 2011-03-04 | 2012-09-05 | 深圳市富恒塑胶新材料有限公司 | Degradable PC (Poly Carbonate)/PLA (Poly Lactic Acid) alloy and preparation method thereof |
| CN104277315A (en) * | 2014-07-10 | 2015-01-14 | 茂泰(福建)鞋材有限公司 | Preparation method of polycarbonate-containing rubber foaming material |
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| CN104277315A (en) * | 2014-07-10 | 2015-01-14 | 茂泰(福建)鞋材有限公司 | Preparation method of polycarbonate-containing rubber foaming material |
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Address after: No. 588, Jinxin Road, Jiangtou Village, Chendai Town, Jinjiang City, Quanzhou City, Fujian Province, 362000 Patentee after: Maotai (Fujian) New Material Technology Co.,Ltd. Address before: 362000 Chen Dai Zhen Jiang tou Cun, Jinjiang City, Quanzhou City, Fujian Province Patentee before: Maotai(Fujian) Soles Co.,Ltd. |
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Application publication date: 20170510 Assignee: Shengtai (Fujian) shoe material Co.,Ltd. Assignor: Maotai (Fujian) New Material Technology Co.,Ltd. Contract record no.: X2023980035563 Denomination of invention: A biodegradable foam sole containing polycarbonate alloy and its preparation method Granted publication date: 20190315 License type: Common License Record date: 20230519 |