CN105153400B - Outdoor shoe bottom microporous polyurethane elastomer - Google Patents
Outdoor shoe bottom microporous polyurethane elastomer Download PDFInfo
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- CN105153400B CN105153400B CN201510370927.9A CN201510370927A CN105153400B CN 105153400 B CN105153400 B CN 105153400B CN 201510370927 A CN201510370927 A CN 201510370927A CN 105153400 B CN105153400 B CN 105153400B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4202—Two or more polyesters of different physical or chemical nature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6283—Polymers of nitrogen containing compounds having carbon-to-carbon double bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0008—Foam properties flexible
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/0066—≥ 150kg/m3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2410/00—Soles
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention relates to a kind of outdoor shoe bottom microporous polyurethane elastomer, formed by isocyanate-reactive component and pre-polymer component reaction；Described isocyanate-reactive component is made up of PEPA A1, PEPA A2, PEPA A3, Isosorbide-5-Nitrae butanediol, MOCA, surface treated filler, diethyl aminoethyl methacrylate, water, catalyst and foam stabilizer；The pre-polymer component is reacted by Carbodiimide-Modified MDI, polyolefin polyhydric alcohol and allyl methacrylate at 75 ~ 85 DEG C, and the pre-polymer component that NCO is 18 ~ 20wt% is made.Outdoor shoe bottom of the present invention microporous polyurethane elastomer has microcellular structure, not only light weight, and elasticity is good；But also maintain higher intensity, wearability and resistance to bend(ing) energy.
Description
Technical field
The present invention relates to the technical field of daily living article material, it is more particularly related to a kind of outdoor shoe
Bottom microporous polyurethane elastomer.
Background technology
Footwear are the necessitys of human lives, and continuing to develop with human civilization, and the species of footwear has also been enriched constantly
Come, the various species such as having playshoes, sport footwear, canvas shoe, chemical footwear, sandals, slippers, medical footwear and safety shoe
Shoes.And the continuous improvement of the development and people's living standard with science and technology, the quality and performance of all kinds of shoes are improved, allows and disappears
Expense person's more safety and comfort are target and the direction of whole shoe-making industry development.According to the report of pertinent literature, shoes weight is every
Increase 100g, the physical consumption of consumer will increase by 1%.In order to reduce physical consumption, snugness of fit is improved, light material is
One of important directions through being developed as material for sole of shoe.Microporous polyurethane elastomer, because its is wear-resisting, lightweight and damping
Performance is good and the characteristic such as easy processing, is also had a wide range of applications in footwear material field.But be used as and be applied to athletic shoe sole
Microporous polyurethane elastomer, although have the advantages that light weight, elasticity are excellent, but the performance such as its tensile strength and tearing strength
Index need further raising, and it usually requires to bond outside it when in use or hot pressing exodermis is used.
The content of the invention
In order to solve the above-mentioned technical problem in the presence of prior art, it is an object of the invention to provide a kind of outdoor shoe
Bottom microporous polyurethane elastomer and the sole being made from it.
In order to solve the above-mentioned technical problem, the invention provides following technical scheme：
A kind of outdoor shoe bottom microporous polyurethane elastomer, by isocyanate-reactive component and pre-polymer component reaction and
Into；Wherein described isocyanate-reactive component is more by the polyester of the PEPA A1 of 35 ~ 40 parts by weight, 4 ~ 5 parts by weight
First alcohol A2,8 ~ 10 parts by weight PEPA A3, the BDO of 5 ~ 6 parts by weight, the 3,3 of 4 ~ 5 parts by weight,- two chloro- 4,
4,- diphenylmethanediamiand（MOCA）, the surface treated filler of 2.0 ~ 2.5 parts by weight, the methyl-prop of 1.8 ~ 2.0 parts by weight
Olefin(e) acid diethylamino ethyl ester, the water of 1.3 ~ 1.5 parts by weight, the catalyst of 0.30 ~ 0.35 parts by weight and 0.25 ~ 0.30 parts by weight
Foam stabilizer composition；The pre-polymer component is by the Carbodiimide-Modified MDI of 35 ~ 40 parts by weight, the polyene of 10 ~ 12 parts by weight
Hydrocarbon polyalcohol and the allyl methacrylate of 2.0 ~ 2.5 parts by weight react at 75 ~ 85 DEG C, and it is 18 ~ 20wt%'s that NCO, which is made,
Pre-polymer component.
Wherein, the PEPA A1 is adipic acid system polyester-diol, and preferably PETA-2000, hydroxyl value is 57 ~ 63
mgKOH/g。
Wherein, the PEPA A2 is aromatic polyester polyol, preferably DH260（The industry trade of Nanjing Daewoo
Company）, its hydroxyl value is 230 ~ 290 mgKOH/g.
Wherein, the PEPA A3 is dipolymer polyester glycol, and (Uniqema is public by preferably Priplast3196
Department), its hydroxyl value is 34 ~ 40 mgKOH/g.
Wherein, the polyolefin polyhydric alcohol is Polybutadiene-acrylonitrile copolymer glycols（HTBN）.
Wherein, described isocyanate-reactive component can also contain antioxidant, foam stabilizer, pigment, Heat-resistant stable
The additives such as agent.
Wherein, the catalyst is at least one of tertiary amines or organo-tin compound or several.Preferably, institute
Catalyst is stated for triethylene diamine, dibutyl tin laurate or stannous octoate.
Wherein, described filler is antiedrite, and its bore dia is 0.35 ~ 0.39 nm, and density is 2.7 ~ 2.8 g/cm3；And
And the antiedrite utilizes the mixed aqueous solution of 5wt% oxalic acid and 5wt% hydrochloric acid to handle 12 ~ 15 hours, then utilizes hydrogen
Sodium oxide molybdena is neutralized to neutrality, is dried after washing, is then calcined 1.5 ~ 2.0 hours at 500 DEG C.
Wherein, described surface treated refers to the processing by following steps：
1) prepare the dimethyl carbonate of the packing quality 200% to 250%, add 20 ~ 30 points of stirring mixing after filler
Clock, obtains premixed slurries；
2) quality is added to for the surface conditioning agent of the packing quality 8 ~ 10% in described premixed slurries, stirring
Mixing 20 ~ 30 minutes, and be ground；
3) slurry after grinding is filtered, and be dried in vacuo in 120 ~ 150 DEG C, you can obtain described warp
The filler of surface treatment.And described surface conditioning agent is the compound with following structure：
In logical formula (I), A is 4- hydroxyethyl imidazoles and the reacted residue of isocyanate groups；R is diphenyl-methane -4,4,-
Part in diisocyanate in addition to isocyanate groups；Wherein, m and n is integer, and 5≤m≤10,3≤n≤5.
Wherein, the compound can be by diphenyl-methane -4,4,The PPG of-diisocyanate and different polymerization degree
First reaction by a certain percentage forms the polyurethane that strand two ends are isocyanate groups in toluene, acetone and other organic solvent,
Add 4- hydroxyethyl imidazoles end-blocking is carried out to it and be prepared, during the course of the reaction, for increase reaction speed, can use pungent
The catalyst commonly used in the polyurethane building-up process such as sour stannous, dibutyl tin laurate.PPG used can be controlled
The degree of polymerization control the m values in formula (), by controlling the mol ratio between PPG and diisocyanate to control
N values in logical formula (I).
The second aspect of the present invention is related to a kind of athletic shoe sole, and described sole is by above-mentioned athletic shoe sole polyurethane
Micro-pore elastomer is made.
Compared with prior art, outdoor shoe bottom of the present invention microporous polyurethane elastomer and the footwear being made from it
Bottom has following beneficial technique effect：Outdoor shoe bottom of the present invention microporous polyurethane elastomer has microcellular structure,
Not only light weight, elastic good；But also maintain higher intensity, wearability and resistance to bend(ing) energy.
Embodiment
Below in conjunction with specific embodiments to outdoor shoe bottom of the present invention microporous polyurethane elastomer and by
Structure, raw material of its sole being made etc. are described in detail, but specific embodiment is not as the restriction to patent of the present invention.
Embodiment 1
Described filler is antiedrite, and its bore dia is 0.35 ~ 0.39 nm, and density is 2.75 g/cm3；And the barium
Zeolite utilizes the mixed aqueous solution of 5wt% oxalic acid and 5wt% hydrochloric acid to handle 15 hours, is then neutralized to using sodium hydroxide
Neutrality, is dried after washing, is then calcined 2.0 hours at 500 DEG C.Described surface treated refers to the place by following steps
Reason：1) prepare the dimethyl carbonate of the packing quality 250%, add stirring mixing 30 minutes after filler, obtain premixing slurry
Material；2) quality is added to for the surface conditioning agent of the filler matter 10% in described premixed slurries, stirring mixing 20 ~ 30
Minute, and be ground；3) slurry after grinding is filtered, and be dried in vacuo in 150 DEG C, you can obtain described
Surface treated filler.And described surface conditioning agent is the compound with following structure：
In logical formula (I), A is 4- hydroxyethyl imidazoles and the reacted residue of isocyanate groups；R is diphenyl-methane -4,4,-
Part in diisocyanate in addition to isocyanate groups；Wherein, m is 8, and n is 3.The compound can be by hexichol first
Alkane -4,4,The PPG of-diisocyanate and different polymerization degree in toluene, acetone and other organic solvent first by a certain percentage
Reaction formed strand two ends be isocyanate groups polyurethane, add 4- hydroxyethyl imidazoles it is carried out end-blocking preparation and
, during the course of the reaction, for increase reaction speed, the polyurethane such as stannous octoate, dibutyl tin laurate can be used to synthesize
During commonly use catalyst.
Comparative example 1
Described filler is antiedrite, and its bore dia is 0.35 ~ 0.39nm, and density is 2.75g/cm3；And the barium boiling
Stone utilizes the mixed aqueous solution of 5wt% oxalic acid and 5wt% hydrochloric acid to handle 15 hours, in being then neutralized to using sodium hydroxide
Property, dried after washing, be then calcined 2.0 hours at 500 DEG C.Described surface treated refers to utilize the ethoxy of 3- aminopropyls three
The processing that base silane is carried out to antiedrite, and the mass ratio of the 3- aminopropyl triethoxysilanes and antiedrite is 1:10.
Comparative example 2
Described filler be graininess nano titanium oxide, its average grain diameter be 20 ~ 50nm, specific surface area be 200 ~
300g/cm2；And the nano titanium oxide is surface-treated using 3- aminopropyl triethoxysilanes, and the 3-
The mass ratio of aminopropyl triethoxysilane and nano titanium oxide is 1:10.
Embodiment 2
The preparation of isocyanate-reactive component：By the adipic acid system polyester-diol PETA-2000 of 35 parts by weight, 5 weight
Part aromatic polyester polyol DH260, the dipolymer polyester glycol Priplast3196 of 8 parts by weight, 2.0 parts by weight through table
The filler of face processing（Filler obtained by embodiment 1）It is added in reactor under conditions of temperature is 90 ~ 100 DEG C, stirring 1
Individual hour, 50 ~ 55 DEG C are cooled to, then add the BDO of 5 parts by weight, the MOCA of 4 parts by weight, the first of 1.8 parts by weight
Base acrylic acid diethylamino ethyl ester, the water of 1.5 parts by weight, the dibutyl tin laurate of 0.30 parts by weight and 0.25 parts by weight
Organosilicon foam stabilizer, be thoroughly mixed it is uniform after discharge, sealing preserve.The preparation of pre-polymer component：By 40 parts by weight
Carbodiimide-Modified MDI, the HTBN of 12 parts by weight, the allyl methacrylate of 2.0 parts by weight is added in reactor
Reacted at 80 DEG C 1.5 ~ 2.0 hours, and detect that the content of NCO bases is protected after 18.0wt%, to be cooled to 40 ~ 50 DEG C of discharging sealings
Deposit.The temperature for controlling isocyanate-reactive component and pre-polymer component is 45 DEG C, and the consumption for adjusting the two causes isocyanates
The ratio between-NCO molal quantity in the active hydrogen molal quantity and pre-polymer component of reactive component is 1：1, then in hybrid chamber
It is quick well mixed, and reaction shaping in the mould that temperature is 50 DEG C is poured into, pressurize is stripped after 5 minutes, then in 80 DEG C of curings
12 hours, you can obtain described microporous polyurethane elastomer.
Embodiment 3
The preparation of isocyanate-reactive component：By the adipic acid system polyester-diol PETA-2000 of 40 parts by weight, 5 weight
Aromatic polyester polyol DH260, the dipolymer polyester glycol Priplast3196 of 10 parts by weight, the warp of 2.5 parts by weight of part
The filler of surface treatment（Filler obtained by embodiment 1）It is added in reactor under conditions of temperature is 90 ~ 100 DEG C, stirs
1 hour is mixed, 50 ~ 55 DEG C are cooled to, the BDO of 6 parts by weight, the MOCA of 4 parts by weight, 2.0 parts by weight are then added
Diethyl aminoethyl methacrylate, the water of 1.5 parts by weight, the dibutyl tin laurate of 0.35 parts by weight and 0.30 weight
The organosilicon foam stabilizer of part is measured, uniform rear discharging, sealing preserve is thoroughly mixed.The preparation of pre-polymer component：By 35 weight
The Carbodiimide-Modified MDI of part, the Polybutadiene-acrylonitrile copolymer glycols of 10 parts by weight（HTBN）, the methyl of 2.0 parts by weight
Allyl acrylate is added in reactor at 80 DEG C 1.5 ~ 2.0 hours of reaction, and detects that the contents of NCO bases is
After 20.0wt%, 40 ~ 50 DEG C of discharging sealing preserves are cooled to.Control the temperature of isocyanate-reactive component and pre-polymer component
For 40 DEG C, active hydrogen molal quantity and the-NCO in pre-polymer component that the consumption of the two causes isocyanate-reactive component are adjusted
The ratio between molal quantity be 1:1, then quickly it is well mixed in hybrid chamber, and pour into temperature to react into 50 DEG C of mould
Type, pressurize is stripped after 5 minutes, then cures 12 hours at 80 DEG C, you can obtain described microporous polyurethane elastomer.
Embodiment 4
The preparation of isocyanate-reactive component：By the adipic acid system polyester-diol PETA-2000 of 38 parts by weight, 5 weight
Aromatic polyester polyol DH260, the dipolymer polyester glycol Priplast3196 of 10 parts by weight, the warp of 2.5 parts by weight of part
The filler of surface treatment（Filler obtained by embodiment 1）It is added in reactor under conditions of temperature is 90 ~ 100 DEG C, stirs
1 hour is mixed, 50 ~ 55 DEG C are cooled to, the BDO of 5 parts by weight is then added, the MOCA of 5 parts by weight, 2.0 parts by weight
Diethyl aminoethyl methacrylate, the water of 1.3 parts by weight, the dibutyl tin laurate of 0.30 parts by weight and 0.25 weight
The organosilicon foam stabilizer of part, is thoroughly mixed uniform rear discharging, sealing preserve.The preparation of pre-polymer component：By 36 parts by weight
Carbodiimide-Modified MDI, the Polybutadiene-acrylonitrile copolymer glycols of 10 parts by weight（HTBN）, the methyl-prop of 2.0 parts by weight
Olefin(e) acid allyl ester is added in reactor 1.5 ~ 2 hours of reaction at 80 DEG C, and detects the content of NCO bases after 20wt%, to drop
Warm to 40 ~ 50 DEG C discharging sealing preserves.The temperature for controlling isocyanate-reactive component and pre-polymer component is 40 DEG C, adjustment two
The consumption of person causes the ratio between-NCO molal quantity in the active hydrogen molal quantity and pre-polymer component of isocyanate-reactive component
For 1:1, then quickly it is well mixed in hybrid chamber, and it is that shaping is reacted in 50 DEG C of mould to pour into temperature, after pressurize 5 minutes
The demoulding, then cures 12 hours at 80 DEG C, you can obtain described microporous polyurethane elastomer.
Comparative example 3
The preparation of isocyanate-reactive component：By the adipic acid system polyester-diol PETA-2000 of 35 parts by weight, 5 weight
Part aromatic polyester polyol DH260, the dipolymer polyester glycol Priplast3196 of 8 parts by weight, 2.0 parts by weight through table
The filler of face processing（Filler obtained by comparative example 1）It is added in reactor under conditions of temperature is 90 ~ 100 DEG C, stirring 1
Individual hour, 50 ~ 55 DEG C are cooled to, then add the BDO of 5 parts by weight, the MOCA of 4 parts by weight, the first of 1.8 parts by weight
Base acrylic acid diethylamino ethyl ester, the water of 1.5 parts by weight, the dibutyl tin laurate of 0.30 parts by weight and 0.25 parts by weight
Organosilicon foam stabilizer, be thoroughly mixed it is uniform after discharge, sealing preserve.The preparation of pre-polymer component：By 40 parts by weight
Carbodiimide-Modified MDI, the HTBN of 12 parts by weight, the allyl methacrylate of 2.0 parts by weight is added in reactor
Reacted at 80 DEG C 1.5 ~ 2.0 hours, and detect that the content of NCO bases is protected after 18.0wt%, to be cooled to 40 ~ 50 DEG C of discharging sealings
Deposit.The temperature for controlling isocyanate-reactive component and pre-polymer component is 45 DEG C, and the consumption for adjusting the two causes isocyanates
The ratio between-NCO molal quantity in the active hydrogen molal quantity and pre-polymer component of reactive component is 1:1, then in hybrid chamber
It is quick well mixed, and reaction shaping in the mould that temperature is 50 DEG C is poured into, pressurize is stripped after 5 minutes, then in 80 DEG C of curings
12 hours, you can obtain microporous polyurethane elastomer.
Comparative example 4
The preparation of isocyanate-reactive component：By the adipic acid system polyester-diol PETA-2000 of 35 parts by weight, 5 weight
Part aromatic polyester polyol DH260, the dipolymer polyester glycol Priplast3196 of 8 parts by weight, 2.0 parts by weight through table
The filler of face processing（Filler obtained by comparative example 2）It is added in reactor under conditions of temperature is 90 ~ 100 DEG C, stirring 1
Individual hour, 50 ~ 55 DEG C are cooled to, then add the BDO of 5 parts by weight, the MOCA of 4 parts by weight, the first of 1.8 parts by weight
Base acrylic acid diethylamino ethyl ester, the water of 1.5 parts by weight, the dibutyl tin laurate of 0.30 parts by weight and 0.25 parts by weight
Organosilicon foam stabilizer, be thoroughly mixed it is uniform after discharge, sealing preserve.The preparation of pre-polymer component：By 40 parts by weight
Carbodiimide-Modified MDI, the HTBN of 12 parts by weight, the allyl methacrylate of 2.0 parts by weight is added in reactor
Reacted at 80 DEG C 1.5 ~ 2.0 hours, and detect that the content of NCO bases is protected after 18.0wt%, to be cooled to 40 ~ 50 DEG C of discharging sealings
Deposit.The temperature for controlling isocyanate-reactive component and pre-polymer component is 45 DEG C, and the consumption for adjusting the two causes isocyanates
The ratio between-NCO molal quantity in the active hydrogen molal quantity and pre-polymer component of reactive component is 1:1, then in hybrid chamber
It is quick well mixed, and reaction shaping in the mould that temperature is 50 DEG C is poured into, pressurize is stripped after 5 minutes, then in 80 DEG C of curings
12 hours, you can obtain microporous polyurethane elastomer.
Comparative example 5
The preparation of isocyanate-reactive component：By the adipic acid system polyester-diol PETA-2000 of 43 parts by weight, 10 weight
The dipolymer polyester glycol Priplast3196 of part, the surface treated filler of 2.5 parts by weight（Filling out obtained by embodiment 1
Material）It is added in reactor under conditions of temperature is 90 ~ 100 DEG C, stirs 1 hour, be cooled to 50 ~ 55 DEG C, then add 5
The BDO of parts by weight, the MOCA of 5 parts by weight, the diethyl aminoethyl methacrylate of 2.0 parts by weight, 1.3 weight
The organosilicon foam stabilizer of the water of part, the dibutyl tin laurate of 0.30 parts by weight and 0.25 parts by weight, is thoroughly mixed
Discharged after even, sealing preserve.The preparation of pre-polymer component：By the Carbodiimide-Modified MDI of 36 parts by weight, 10 parts by weight it is poly-
Butadiene-acrylonitrile copolymer glycol（HTBN）, the allyl methacrylate of 2.0 parts by weight is added in reactor at 80 DEG C
React 1.5 ~ 2 hours, and detect the content of NCO bases after 20wt%, to be cooled to 40 ~ 50 DEG C of discharging sealing preserves.Control isocyanide
The temperature of acid esters reactive component and pre-polymer component is 40 DEG C, and the consumption for adjusting the two causes isocyanate-reactive component
The ratio between-NCO molal quantity in active hydrogen molal quantity and pre-polymer component is 1:1, then quickly it is well mixed in hybrid chamber,
And reaction shaping in the mould that temperature is 50 DEG C is poured into, pressurize is stripped after 5 minutes, then cures 12 hours at 80 DEG C, you can
Obtain microporous polyurethane elastomer.
Comparative example 6
The preparation of isocyanate-reactive component：By the adipic acid system polyester-diol PETA-2000 of 48 parts by weight, 5 weight
The aromatic polyester polyol DH260, the surface treated filler of 2.5 parts by weight of part（Filler obtained by embodiment 1）Plus
Enter into reactor under conditions of temperature is 90 ~ 100 DEG C, stir 1 hour, be cooled to 50 ~ 55 DEG C, then add 5 weight
The BDO of part, the MOCA of 5 parts by weight, the diethyl aminoethyl methacrylate of 2.0 parts by weight, 1.3 parts by weight
The organosilicon foam stabilizer of water, the dibutyl tin laurate of 0.30 parts by weight and 0.25 parts by weight, after being thoroughly mixed uniformly
Discharging, sealing preserve.The preparation of pre-polymer component：By the Carbodiimide-Modified MDI of 36 parts by weight, the polybutadiene of 10 parts by weight
Alkene-acrylonitrile compolymer glycol（HTBN）, the allyl methacrylate of 2.0 parts by weight is added in reactor to react at 80 DEG C
1.5 ~ 2 hours, and detect the content of NCO bases after 20wt%, to be cooled to 40 ~ 50 DEG C of discharging sealing preserves.Control isocyanates
The temperature of reactive component and pre-polymer component is 40 DEG C, adjusts the consumption of the two and causes the active of isocyanate-reactive component
The ratio between-NCO molal quantity in hydrogen molal quantity and pre-polymer component is 1:1, then quickly it is well mixed in hybrid chamber, and pour
Enter and shaping is reacted in the mould that temperature is 50 DEG C, pressurize is stripped after 5 minutes, then cures 12 hours at 80 DEG C, you can obtain
Microporous polyurethane elastomer.
Comparative example 7
The preparation of isocyanate-reactive component：By the adipic acid system polyester-diol PETA-2000 of 38 parts by weight, 5 weight
Aromatic polyester polyol DH260, the dipolymer polyester glycol Priplast3196 of 10 parts by weight, the warp of 2.5 parts by weight of part
The filler of surface treatment（Filler obtained by embodiment 1）It is added in reactor under conditions of temperature is 90 ~ 100 DEG C, stirs
1 hour is mixed, 50 ~ 55 DEG C are cooled to, the BDO of 5 parts by weight is then added, the MOCA of 5 parts by weight, 2.0 parts by weight
Diethyl aminoethyl methacrylate, the water of 1.3 parts by weight, the dibutyl tin laurate of 0.30 parts by weight and 0.25 weight
The organosilicon foam stabilizer of part, is thoroughly mixed uniform rear discharging, sealing preserve.The preparation of pre-polymer component：By 36 parts by weight
Carbodiimide-Modified MDI, the allyl methacrylates of 2.0 parts by weight be added in reactor at 80 DEG C reaction 1.5 ~
2 hours, and detect the content of NCO bases after 20wt%, to be cooled to 40 ~ 50 DEG C of discharging sealing preserves.Control isocyanates reaction
Property component and pre-polymer component temperature be 40 DEG C, adjust the consumption of the two so that the active hydrogen of isocyanate-reactive component rubs
The ratio between-NCO molal quantity in that number and pre-polymer component is 1:1, then quickly it is well mixed in hybrid chamber, and pour into temperature
Spend and shaping is reacted in the mould for 50 DEG C, pressurize is stripped after 5 minutes, then cures 12 hours at 80 DEG C, you can obtain poly- ammonia
Ester micro-pore elastomer.
The performance for the microporous polyurethane elastomer that embodiment 2 ~ 4 and comparative example 3 ~ 7 are prepared is as shown in table 1：
Table 1
It the foregoing is only the preferred embodiments of the present invention, it is impossible to be construed to limit the scope of the present invention with this, it is all at this
The equivalent deformation made in the claimed scope of claims of invention and the embodiment of change are in the present invention
In claimed scope.
Claims (3)
1. a kind of outdoor shoe bottom microporous polyurethane elastomer, by isocyanate-reactive component and pre-polymer component reaction
Into；It is characterized in that：PEPA A1 of the described isocyanate-reactive component by 35~40 parts by weight, 4~5 parts by weight
PEPA A2, the PEPA A3 of 8~10 parts by weight, the BDO of 5~6 parts by weight, 4~5 parts by weight
3,3 ,-two chloro- 4,4 ,-diphenylmethanediamiand (MOCA), the surface treated filler of 2.0~2.5 parts by weight, 1.8~2.0
The diethyl aminoethyl methacrylate of parts by weight, the water of 1.3~1.5 parts by weight, the catalyst of 0.30~0.35 parts by weight
Constituted with the foam stabilizer of 0.25~0.30 parts by weight；The pre-polymer component by 35~40 parts by weight Carbodiimide-Modified
The allyl methacrylate of MDI, the polyolefin polyhydric alcohol of 10~12 parts by weight and 2.0~2.5 parts by weight is at 75~85 DEG C
Reaction, is made the pre-polymer component that NCO is 18~20wt%；Wherein, the PEPA A1 is adipic acid system polyester-diol
PETA-2000, hydroxyl value is 57~63mgKOH/g, and the PEPA A2 is that the aromatic polyester that the trade mark is DH260 is polynary
Alcohol, and its hydroxyl value is 230~290mgKOH/g, the PEPA A3 is the dimer polyester that the trade mark is Priplast3196
Glycol, and its hydroxyl value is 34~40mgKOH/g, the polyolefin polyhydric alcohol is Polybutadiene-acrylonitrile copolymer glycols；It is described to fill out
Expect for antiedrite, its bore dia is 0.35~0.39nm, density is 2.7~2.8g/cm3；And the antiedrite utilizes 5wt%
Oxalic acid and 5wt% hydrochloric acid mixed aqueous solution handle 12~15 hours, be then neutralized to neutrality using sodium hydroxide, wash
Dried after washing, be then calcined 1.5~2.0 hours at 500 DEG C；Described surface treated refers to the processing by following steps
It is modified：
1) prepare the dimethyl carbonate of the packing quality 200% to 250%, add stirring mixing 20~30 minutes after filler,
Obtain premixed slurries；
2) quality is added to for the surface conditioning agent of the packing quality 8~10% in described premixed slurries, stirring is mixed
Close 20~30 minutes, and be ground；
3) slurry after grinding is filtered, and be dried in vacuo in 120~150 DEG C, you can obtain described through surface
The filler of processing；And described surface conditioning agent is the compound with following structure：
In logical formula (I), A is 4- hydroxyethyl imidazoles and the reacted residue of isocyanate groups；R is diphenyl-methane -4,4, and-two is different
Part in cyanate in addition to isocyanate groups；Wherein, m and n is integer, and 5≤m≤10,3≤n≤5.
2. outdoor shoe bottom according to claim 1 microporous polyurethane elastomer, it is characterised in that：Described isocyanates
Reactive component also includes at least one of antioxidant, foam stabilizer, pigment or heat-resisting stabilizing agent.
3. a kind of athletic shoe sole, it is characterised in that：Described sole is as the microporous polyurethane described in claim any one of 1-2
Elastomer is made.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102115588A (en) * | 2009-12-31 | 2011-07-06 | 浙江华峰新材料股份有限公司 | Polyurethane microporous elastomer with characteristics of rubber and preparation method thereof |
| CN103570908A (en) * | 2012-07-19 | 2014-02-12 | 旭川化学（昆山）有限公司 | Polyurethane sole material raw liquid |
| CN103570907A (en) * | 2012-07-19 | 2014-02-12 | 旭川化学（昆山）有限公司 | Low temperature resistance polyurethane sole material |
| CN104072716A (en) * | 2014-07-18 | 2014-10-01 | 浙江奥康鞋业股份有限公司 | Polyurethane elastomer and sole made from same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104031478B (en) * | 2014-07-03 | 2016-04-13 | 苏州世名科技股份有限公司 | Painted pigment dyestuff aqueous color paste of a kind of synthetic leather and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102115588A (en) * | 2009-12-31 | 2011-07-06 | 浙江华峰新材料股份有限公司 | Polyurethane microporous elastomer with characteristics of rubber and preparation method thereof |
| CN103570908A (en) * | 2012-07-19 | 2014-02-12 | 旭川化学（昆山）有限公司 | Polyurethane sole material raw liquid |
| CN103570907A (en) * | 2012-07-19 | 2014-02-12 | 旭川化学（昆山）有限公司 | Low temperature resistance polyurethane sole material |
| CN104072716A (en) * | 2014-07-18 | 2014-10-01 | 浙江奥康鞋业股份有限公司 | Polyurethane elastomer and sole made from same |
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Effective date of registration: 20190507 Address after: 342700 Ancient Camphor Industrial Park, Shicheng County, Ganzhou City, Jiangxi Province Patentee after: Ganzhou Blue Fish Shoes Co., Ltd. Address before: Room 2203, Building 6, Lanwan Peninsula, Zhongjun, Xingxia Road, Qidian Town, Jinjiang City, Fujian Province, 362000 Patentee before: JINJIANG CITY CHIDIAN TOWN JIAOPENG TRADE CO., LTD. |
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Denomination of invention: Polyurethane microporous elastomer for outdoor sole Effective date of registration: 20200728 Granted publication date: 20170804 Pledgee: Urban sub branch of Jiangxi Shicheng Rural Commercial Bank Co., Ltd Pledgor: Ganzhou Blue Fish Shoes Co.,Ltd. Registration number: Y2020360000069 |