CN109438671A - Polyurethane stock solution and preparation method and application containing herb powder - Google Patents
Polyurethane stock solution and preparation method and application containing herb powder Download PDFInfo
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- CN109438671A CN109438671A CN201811196911.0A CN201811196911A CN109438671A CN 109438671 A CN109438671 A CN 109438671A CN 201811196911 A CN201811196911 A CN 201811196911A CN 109438671 A CN109438671 A CN 109438671A
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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
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B17/00—Insoles for insertion, e.g. footbeds or inlays, for attachment to the shoe after the upper has been joined
- A43B17/14—Insoles for insertion, e.g. footbeds or inlays, for attachment to the shoe after the upper has been joined made of sponge, rubber, or plastic materials
-
- 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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/282—Alkanols, cycloalkanols or arylalkanols including terpenealcohols
- C08G18/2825—Alkanols, cycloalkanols or arylalkanols including terpenealcohols having at least 6 carbon atoms
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3275—Hydroxyamines containing two hydroxy groups
-
- 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
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- 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
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
-
- 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
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
-
- 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
- C08K5/00—Use of organic ingredients
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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
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
Abstract
The invention discloses a kind of polyurethane stock solution and preparation method and application containing herb powder, the polyurethane stock solution containing herb powder includes: the polyol-mixture component A containing physical property reinforcing agent；Isocyanate prepolymers body component B and herb powder C, physical property reinforcing agent are one or more of glycol amines or Long carbon chain monohydric alcohol of the branch containing chain alkyl.The present invention is obvious for the physical property promotion effect of the polyurethane insole containing herb powder, and Chinese medicine health-care polyurethane insole not only has Chinese medicine health-care effect, but also the physical mechanical properties such as tearing strength and tensile strength are high, long service life.
Description
Technical field
The present invention relates to a kind of polyurethane stock solution and preparation method and application containing herb powder.
Background technique
Health begins in, and foot is made of 26 pieces of bones, is dispersed with 76 acupuncture points, is the second heart or the people of human body
The weight bearing organ and locomotive organ of body are that the most tired part of human body, foot health-care and comfortable Journal of Sex Research anticipate to the health of human body
Justice is important.Insole has the function of that slow weight, damping, moisture absorption are breathed freely, adjustable vola due to long-term stress caused by it is uncomfortable,
Alleviate foot pressure.With the development of science and technology the material of insole is enriched constantly.From insole of fabric shoes, EVA shoe pad to polyurethane insole etc.
Various materials are dazzling.Functionally, the functional insoles such as ventilative, Chinese medicine health-care of moisture absorption are also deep is favored by market.By
Traditional Chinese medicine ingredients are added in insole and play health-care efficacy, and such as 201610126552.6,201610126553.0 patent applications disclose
It is a kind of to have effects that the flexible polyurethane foams of Chinese medicine therapy, Chinese medicine is ground into thick end, is mixed with part polyalcohol, then will hair
One or more of infusion and catalyst, foam stabiliser, fire retardant, pigment are successively sufficiently mixed with another part polyalcohol
Stirring, then with isocyanate component mixed foaming, curing molding, wherein the additional amount of herb powder accounts for the 10wt%- of total amount
20wt%.Herb powder is added in soft polyurethane foam by this method is made Chinese medicine health-care polyurethane insole, but obtained Chinese medicine
Health care polyurethane insole is due to the addition of herb powder, and physical mechanical property loss is obvious, and especially tearing strength, tension are strong
Degree etc. is difficult to meet long-time service requirement.
Summary of the invention
The object of the present invention is to provide a kind of polyurethane stock solution and preparation method and application containing herb powder, to solve
The shortcomings of the prior art.
Polyurethane stock solution of the present invention containing herb powder includes:
Polyol-mixture component A containing physical property reinforcing agent；
Isocyanate prepolymers body component B and
Herb powder C；
The additive amount of the herb powder C is 5wt%~20wt% of the polyol-mixture component A gross mass；
The dosage of physical property reinforcing agent is the 0.5wt%-7.0wt% of polyol-mixture component A gross mass；
The physical property reinforcing agent is one or more of glycol amines or Long carbon chain monohydric alcohol of the branch containing chain alkyl；
In the polyurethane stock solution containing herb powder, the polyol-mixture component A containing physical property reinforcing agent with it is different
The mass ratio of cyanate performed polymer component B is 10:7~5:6；
The herb powder C is mulberry leaf, feverfew, Prunella vulgaris, radix scutellariae, Yellow Fructus Gardeniae, late silkworm excrement, the root bark of tree peony, the root of Dahurain angelica, peppermint
In leaf, cassia seed, radix cyathulae, alum, the achene of Siberian cocklebur, Flos Magnoliae Liliflorae, dried orange peel, Pogostemon cablin, perilla leaf, honeysuckle, Flos Albiziae or honeysuckle
One or more powder, the partial size of herb powder is 100 mesh or more；
Preferably, the polyol-mixture component A containing physical property reinforcing agent, the group including following mass percentage
Point:
In the Isocyanate prepolymers body component B, the mass percentage of each raw material are as follows:
MDI-100 40%~58%
Carbodiimide-Modified MDI 2%~10%
Polyether polyol 40%~50%；
It preferably, also include phosphoric acid in the Isocyanate prepolymers body component B, the additional amount of the phosphoric acid is isocyanic acid
0.0020wt%~0.0060wt% of ester performed polymer component B；
The polyether polyol is with one or more of ethylene glycol, diglycol or glycerine for initiator,
It is copolymerized to obtain with ethylene oxide by the ring-opening polymerisation of 1,2- propylene oxide or propylene oxide, degree of functionality is 2~3, and number-average molecular weight is
2000~7000, preferably polyether polyol 330N, polyether polyol 360N, polyether polyol TED-28, polyether polyol
One or more of KE-810 or polyether polyol KE-804.
The chain extender be ethylene glycol, 1,4-butanediol, diglycol, 1,3-PD, dipropylene glycol, two
One or more of contracting triethylene glycol, tripropylene glycol；
Preferably, the physical property reinforcing agent is the glycol amines and Long carbon chain monohydric alcohol of the branch containing chain alkyl
Mixture, mass ratio are 1:9~9:1；
Preferably, the glycol amines of the branch containing chain alkyl are N- alkyl diethanol amine；
The skeleton symbol of the N- alkyl diethanol amine are as follows:
The Long carbon chain monohydric alcohol is one or more of lauryl alcohol, tetradecyl alchohol, hexadecanol and octadecyl alcolol；
Preferably, the Long carbon chain monohydric alcohol is in lauryl alcohol, tetradecyl alchohol, hexadecanol and the octadecyl alcolol of straight chain linear structure
More than one；
The foaming agent is water；
The foam stabilizer is organic silicon surfactant；
The catalyst is the ethylene glycol solution that mass concentration is 33% triethylene diamine, in bis- (dimethylaminoethyl) ethers
One or two kinds of mixtures；
The pore-creating agent is polypropylene oxide-ethylene oxide copolyether, one in polyoxygenated alkene-polysiloxane copolymer
Kind or more；
The MDI-100 isocyanates is 4,4 ' -99% or more methyl diphenylene diisocyanate contents；
The Carbodiimide-Modified MDI is carbodiimide modified diphenylmethane diisocyanate；
The preparation method of the polyurethane stock solution containing herb powder, includes the following steps:
(1) by polyether polyol, chain extender, physical property reinforcing agent, foaming agent, foam stabilizer, catalyst, pore-creating agent (25~
DEG C 45) (2.5~3.5) h is mixed at, discharging is sealed, and obtains the polyol blends group containing physical property reinforcing agent
Divide A spare；
(2) it is spare to weigh herb powder C；
(3) MDI-100, Carbodiimide-Modified MDI, phosphoric acid, polyether polyol reacted to 2.0 at 60~70 DEG C~
It is spare to obtain the Isocyanate prepolymers body component B by 3.0h；
The polyether-polyurethane stoste containing herb powder, can be used for preparing the Chinese medicine health-care polyurethane shoe of high physical property
Pad, application method are as follows:
The herb powder C is added in the polyol-mixture component A containing physical property reinforcing agent and is mixed, is contained
The polyol-mixture component A containing physical property reinforcing agent of herb powder C, and maintain its temperature at 20~30 DEG C；
The temperature of Isocyanate prepolymers body component B is 20~30 DEG C；
Two components that above-mentioned steps are obtained mix, and injection temperature is reaction 4~6min molding in 40~50 DEG C of molds,
Demoulding cures 45~50h, obtains the Chinese medicine health-care polyurethane insole of high physical property；
The polyol blends containing physical property reinforcing agent are added in the herb powder C by another method of the invention
Component includes the polyol blends group containing physical property reinforcing agent and herb powder that is, containing the polyurethane stock solution of herb powder
Divide and Isocyanate prepolymers body component；
Compared with prior art, the invention has the following advantages:
(1) the Long carbon chain monohydric alcohol of the glycol amines and straight chain linear structure that use the branch containing chain alkyl is compounded as object
Property reinforcing agent when, for the polyurethane insole containing herb powder physical property promoted effect become apparent from.
(2) Chinese medicine health-care polyurethane insole of the present invention not only has a Chinese medicine health-care effect, and tearing strength and
The physical mechanical properties such as tensile strength are high, long service life.
Specific embodiment
Below by specific embodiment, the present invention is further elaborated, it should be understood that reality of the invention
Specific material proportion described in example is applied, process conditions and result are merely to illustrate the present invention, this can not be limited with this
The protection scope of invention, the equivalent change or modification that all Spirit Essences according to the present invention are done, should all cover in this hair
In bright protection scope.
In embodiment:
Polyether polyol 330N uses the Shandong blue star Dong great Co., Ltd trade mark for the product of EP-330N；
Polyether polyol TED-28 uses the three petrochemical industry Co., Ltd trade mark of Tianjin for the product of TED-28；
Embodiment 1
(1) by the polyether polyol 330N of 8.50kg (33~37mgKOH/g of hydroxyl value), the ethylene glycol of 0.40kg, 0.055kg
(HO)2N(CH2)11CH3, the straight chain linear structure lauryl alcohol of 0.495kg, the water of 0.15kg, 0.10kg organosilicon foam stabilizer
The ethylene glycol solution of 33% triethylene diamine of pore-creating agent HF-350D, 0.10kg of L-580,0.20kg mixes at 25 DEG C
3.5h, discharging are sealed, and obtain the polyol-mixture component containing physical property reinforcing agent；
(2) Baical Skullcap Root (100 mesh of partial size) of 1.50kg is weighed；The physical property that contains that step (1) obtains is added it to increase
In the polyol-mixture component of strong agent, it is uniformly mixed；
(3) by the carbodiimide modified diphenylmethane diisocyanate of MDI-100,0.20kg of 5.80kg, 0.20g
Phosphoric acid, 4.0kg polyether polyol 330N (33~37mgKOH/g of hydroxyl value) react 3.0h at 60 DEG C, obtain isocyano
The base polyurethane prepolymer for use as component of sealing end；
(4) maintain the component of mixture temperature of step (2) at 20 DEG C, the base polyurethane prepolymer for use as component temperature of isocyano sealing end
Two components are sufficiently mixed by degree at 20 DEG C, inject 40 DEG C of mold reaction 6min moldings, and demoulding cures 50h, obtains containing Chinese medicine
The high performance polyurethane insole of powder.
Embodiment 2
(1) by the 1,4-butanediol of the polyether polyol TED-28 of 8.00kg (24~26mgKOH/g of hydroxyl value), 0.80kg,
(HO) of 0.63kg2N(CH2)13CH3, straight chain linear structure hexadecanol, the water of 0.10kg, the organosilicon of 0.10kg of 0.07kg it is even
The ethylene glycol solution of 33% triethylene diamine of pore-creating agent CHK350D, 0.10kg of infusion DC-193,0.20kg mixes at 35 DEG C
3.0h is closed, discharging is sealed, and obtains the polyol-mixture component containing physical property reinforcing agent；
(2) Dahurian Angelica Root (200 mesh of partial size) of 2.00kg is weighed；The physical property that contains that step (1) obtains is added it to increase
In the polyol-mixture component of strong agent, it is uniformly mixed；
(3) by the carbodiimide modified diphenylmethane diisocyanate of MDI-100,1.13kg of 5.65kg, 0.26g
Phosphoric acid, 4.52kg polyether polyol TED-28 (24~26mgKOH/g of hydroxyl value) react 2.0h at 70 DEG C, obtain isocyanic acid
The base polyurethane prepolymer for use as component of root sealing end；
(4) maintain the component of mixture temperature of step (2) at 20 DEG C, the base polyurethane prepolymer for use as component temperature of isocyano sealing end
Two components are sufficiently mixed by degree at 20 DEG C, inject 50 DEG C of mold reaction 4min moldings, and demoulding cures 45h, obtains containing Chinese medicine
The high performance polyurethane insole of powder.
Embodiment 3
(1) by the 1,4-butanediol of the polyether polyol TED-28 of 8.00kg (24~26mgKOH/g of hydroxyl value), 0.80kg,
(HO) of 0.70kg2N(CH2)13CH3, the water of 0.10kg, 0.10kg organosilicon foam stabilizer DC-193,0.20kg pore-creating agent
The ethylene glycol solution of 33% triethylene diamine of CHK350D, 0.10kg mixes 3.0h at 35 DEG C, and discharging is sealed, and obtains
Polyol-mixture component containing physical property reinforcing agent；
(2) Dahurian Angelica Root (200 mesh of partial size) of 2.00kg is weighed；The physical property that contains that step (1) obtains is added it to increase
In the polyol-mixture component of strong agent, it is uniformly mixed；
(3) by the carbodiimide modified diphenylmethane diisocyanate of MDI-100,1.17kg of 5.86kg, 0.27g
Phosphoric acid, 4.69kg polyether polyol TED-28 (24~26mgKOH/g of hydroxyl value) react 2.0h at 70 DEG C, obtain isocyanic acid
The base polyurethane prepolymer for use as component of root sealing end；
(4) maintain the component of mixture temperature of step (2) at 20 DEG C, the base polyurethane prepolymer for use as component temperature of isocyano sealing end
Two components are sufficiently mixed by degree at 20 DEG C, inject 50 DEG C of mold reaction 4min moldings, and demoulding cures 45h, obtains containing Chinese medicine
The high performance polyurethane insole of powder.
Embodiment 4
(1) by the 1,4-butanediol of the polyether polyol TED-28 of 8.00kg (24~26mgKOH/g of hydroxyl value), 0.80kg,
The straight chain linear structure hexadecanol of 0.70kg, the water of 0.10kg, 0.10kg organosilicon foam stabilizer DC-193,0.20kg aperture
The ethylene glycol solution of 33% triethylene diamine of agent CHK350D, 0.10kg mixes 3.0h at 35 DEG C, and discharging is sealed, and obtains
To the polyol-mixture component containing physical property reinforcing agent；
(2) Dahurian Angelica Root (200 mesh of partial size) of 2.00kg is weighed；The physical property that contains that step (1) obtains is added it to increase
In the polyol-mixture component of strong agent, it is uniformly mixed；
(3) by the carbodiimide modified diphenylmethane diisocyanate of MDI-100,1.09kg of 5.43kg, 0.25g
Phosphoric acid, 4.34kg polyether polyol TED-28 (24~26mgKOH/g of hydroxyl value) react 2.0h at 70 DEG C, obtain isocyanic acid
The base polyurethane prepolymer for use as component of root sealing end；
(4) maintain the component of mixture temperature of step (2) at 20 DEG C, the base polyurethane prepolymer for use as component temperature of isocyano sealing end
Two components are sufficiently mixed by degree at 20 DEG C, inject 50 DEG C of mold reaction 4min moldings, and demoulding cures 45h, obtains containing Chinese medicine
The high performance polyurethane insole of powder.
Embodiment 5
(1) by the polyether polyol 330N of 9.50kg (33~37mgKOH/g of hydroxyl value), the ethylene glycol of 0.10kg, 0.02kg
(HO)2N(CH2)17CH3, the straight chain linear structure octadecyl alcolol of 0.03kg, the water of 0.19kg, 0.05kg organosilicon foam stabilizer L-
580, the ethylene glycol solution of 33% triethylene diamine of pore-creating agent CHK350A, 0.06kg of 0.05kg mixes 2.5h at 40 DEG C,
Discharging is sealed, and obtains the polyol-mixture component containing physical property reinforcing agent；
(2) Siberian Cocklebur Fruit (300 mesh of partial size) of 0.50kg is weighed；Add it to that step (1) obtains contains physical property
In the polyol-mixture component of reinforcing agent, it is uniformly mixed；
(3) by the carbodiimide modified diphenylmethane diisocyanate of MDI-100,0.71kg of 2.84kg, 0.18g
Phosphoric acid, 3.55kg polyether polyol TED-28 (24~26mgKOH/g of hydroxyl value) react 3.0h at 60 DEG C, obtain isocyanic acid
The base polyurethane prepolymer for use as component of root sealing end；
(4) maintain the component of mixture temperature of step (2) at 30 DEG C, the base polyurethane prepolymer for use as component temperature of isocyano sealing end
Two components are sufficiently mixed by degree at 30 DEG C, inject 45 DEG C of mold reaction 5min moldings, and demoulding cures 48h, obtains containing Chinese medicine
The high performance polyurethane insole of powder.
Embodiment 6
(1) by the polyether polyol TED-28 of 9.00kg (24~26mgKOH/g of hydroxyl value), 0.10kg ethylene glycol,
(HO) of the 1,4- butanediol of 0.10kg, 0.27kg2N(CH2)17CH3, the straight chain linear structure octadecyl alcolol of 0.03kg, 0.20kg
Water, 0.10kg organosilicon foam stabilizer L-580,0.10kg pore-creating agent CHK350A, 0.10kg 33% triethylene diamine second
Glycol solution mixes 2.5h at 40 DEG C, and discharging is sealed, and obtains the polyol-mixture component containing physical property reinforcing agent；
(2) Siberian Cocklebur Fruit (300 mesh of partial size) of 1.00kg is weighed；Add it to that step (1) obtains contains physical property
In the polyol-mixture component of reinforcing agent, it is uniformly mixed；
(3) by the carbodiimide modified diphenylmethane diisocyanate of MDI-100,0.83kg of 3.32kg, 0.21g
Phosphoric acid, 4.14kg polyether polyol TED-28 (24~26mgKOH/g of hydroxyl value) react 3.0h at 60 DEG C, obtain isocyanic acid
The base polyurethane prepolymer for use as component of root sealing end；
(4) maintain the component of mixture temperature of step (2) at 30 DEG C, the base polyurethane prepolymer for use as component temperature of isocyano sealing end
Two components are sufficiently mixed by degree at 30 DEG C, inject 45 DEG C of mold reaction 5min moldings, and demoulding cures 48h, obtains containing Chinese medicine
The high performance polyurethane insole of powder.
Embodiment 7
(1) by the polyether polyol TED-28 of 9.00kg (24~26mgKOH/g of hydroxyl value), 0.10kg ethylene glycol,
(HO) of the 1,4- butanediol of 0.10kg, 0.27kg2N(CH2)17CH3, the non-straight chain structure octadecyl alcolol of 0.03kg, 0.20kg
Water, 0.10kg organosilicon foam stabilizer L-580,0.10kg pore-creating agent CHK350A, 0.10kg 33% triethylene diamine second
Glycol solution mixes 2.5h at 40 DEG C, and discharging is sealed, and obtains the polyol-mixture component containing physical property reinforcing agent；
(2) Siberian Cocklebur Fruit (300 mesh of partial size) of 1.00kg is weighed；Add it to that step (1) obtains contains physical property
In the polyol-mixture component of reinforcing agent, it is uniformly mixed；
(3) by the carbodiimide modified diphenylmethane diisocyanate of MDI-100,0.83kg of 3.32kg, 0.21g
Phosphoric acid, 4.14kg polyether polyol TED-28 (24~26mgKOH/g of hydroxyl value) react 3.0h at 60 DEG C, obtain isocyanic acid
The base polyurethane prepolymer for use as component of root sealing end；
(4) maintain the component of mixture temperature of step (2) at 30 DEG C, the base polyurethane prepolymer for use as component temperature of isocyano sealing end
Two components are sufficiently mixed by degree at 30 DEG C, inject 45 DEG C of mold reaction 5min moldings, and demoulding cures 48h, obtains containing Chinese medicine
The high performance polyurethane insole of powder.
Comparative example 1
(1) by the ethylene glycol of the polyether polyol 330N of 8.50kg (33~37mgKOH/g of hydroxyl value), 0.40kg, 0.055kg
(HO)2N(CH2)11CH3, the straight chain linear structure lauryl alcohol of 0.495kg, the water of 0.15kg, 0.10kg organosilicon foam stabilizer
The ethylene glycol solution of 33% triethylene diamine of pore-creating agent HF-350D, 0.10kg of L-580,0.20kg mixes at 25 DEG C
3.5h, discharging are sealed, and obtain the polyol-mixture component containing physical property reinforcing agent；
(2) Baical Skullcap Root (100 mesh of partial size) of 1.50kg is weighed；The physical property that contains that step (1) obtains is added it to increase
In the polyol-mixture component of strong agent, it is uniformly mixed；
(3) by the phosphoric acid of MDI-100,0.20g of 6.0kg, 4.0kg polyether polyol 330N (hydroxyl value 33~
3.0h 37mgKOH/g) is reacted at 60 DEG C, obtains isocyano
Comparative example 2
(1) by the polyether polyol TED-28 of 8.00kg (24~26mgKOH/g of hydroxyl value), 0.80kg 1,4- butanediol,
33% 3 second of the water of 0.10kg, pore-creating agent CHK350D, 0.10kg of organosilicon foam stabilizer DC-193,0.20kg of 0.10kg
The ethylene glycol solution of alkene diamines mixes 3.0h at 35 DEG C, and discharging is sealed, and obtains polyol-mixture component；
(2) Dahurian Angelica Root (200 mesh of partial size) of 2.00kg is weighed；Add it to the polyalcohol mixing that step (1) obtains
In object component, it is uniformly mixed；
(3) by the carbodiimide modified diphenylmethane diisocyanate of MDI-100,1.01kg of 5.06kg, 0.26g
Phosphoric acid, 4.05kg polyether polyol TED-28 (24~26mgKOH/g of hydroxyl value) react 2.0h at 70 DEG C, obtain isocyanic acid
The base polyurethane prepolymer for use as component of root sealing end；
(4) maintain the component of mixture temperature of step (2) at 20 DEG C, the base polyurethane prepolymer for use as component temperature of isocyano sealing end
Two components are sufficiently mixed by degree at 20 DEG C, inject 50 DEG C of mold reaction 4min moldings, and demoulding cures 45h, obtains containing Chinese medicine
The polyurethane insole of powder.
Comparative example 3
(1) by the polyether polyol 330N of 9.50kg (33~37mgKOH/g of hydroxyl value), the ethylene glycol of 0.10kg, 0.19kg
Water, 0.05kg organosilicon foam stabilizer L-580,0.05kg pore-creating agent CHK350A, 0.06kg 33% triethylene diamine
Ethylene glycol solution mixes 2.5h at 40 DEG C, and discharging is sealed, and obtains polyol-mixture component；
(2) Siberian Cocklebur Fruit (300 mesh of partial size) of 0.50kg is weighed；It is mixed to add it to the polyalcohol that step (1) obtains
In polymer component, it is uniformly mixed；
(3) by the carbodiimide modified diphenylmethane diisocyanate of MDI-100,0.71kg of 2.84kg, 0.18g
Phosphoric acid, 3.55kg polyether polyol TED-28 (24~26mgKOH/g of hydroxyl value) react 3.0h at 60 DEG C, obtain isocyanic acid
The base polyurethane prepolymer for use as component of root sealing end；
(4) maintain the component of mixture temperature of step (2) at 30 DEG C, the base polyurethane prepolymer for use as component temperature of isocyano sealing end
Two components are sufficiently mixed by degree at 30 DEG C, inject 45 DEG C of mold reaction 5min moldings, and demoulding cures 48h, obtains containing Chinese medicine
The polyurethane insole of powder.
Comparative example 4
(1) by the polyether polyol TED-28 of 9.00kg (24~26mgKOH/g of hydroxyl value), 0.10kg ethylene glycol,
The 1,4- butanediol of 0.10kg, the water of 0.20kg, 0.10kg organosilicon foam stabilizer L-580,0.10kg pore-creating agent
The ethylene glycol solution of 33% triethylene diamine of CHK350A, 0.10kg mixes 2.5h at 40 DEG C, and discharging is sealed, and obtains
Polyol-mixture component；
(2) Siberian Cocklebur Fruit (300 mesh of partial size) of 1.00kg is weighed；It is mixed to add it to the polyalcohol that step (1) obtains
In polymer component, it is uniformly mixed；
(3) by the carbodiimide modified diphenylmethane diisocyanate of MDI-100,0.78kg of 3.14kg, 0.20g
Phosphoric acid, 3.91kg polyether polyol TED-28 (24~26mgKOH/g of hydroxyl value) react 3.0h at 60 DEG C, obtain isocyanic acid
The base polyurethane prepolymer for use as component of root sealing end；
(4) maintain the component of mixture temperature of step (2) at 30 DEG C, the base polyurethane prepolymer for use as component temperature of isocyano sealing end
Two components are sufficiently mixed by degree at 30 DEG C, inject 45 DEG C of mold reaction 5min moldings, and demoulding cures 48h, obtains containing Chinese medicine
The polyurethane insole of powder.
Every physical property measurement result of polyurethane insole obtained by Application Example 1~6 and comparative example 1~4 is listed in table
1。
Table 1
Wherein, the test of compact density presses HG/T2489- at the test of type hardness tester by the regulation of GB/T 6343-2009
2007 regulation, tensile strength and elongation by GB/T 528 regulation, tearing strength by GB/T 529 regulation.
As shown in Table 1, herb powder is added in polyurethane system the present invention, assigns polyurethane insole Chinese medicine health-care and makees
With the addition physical property reinforcing agent in polyurethane system improves the synthesis physical property of Chinese medicine health-care polyurethane insole, and using containing long-chain
The glycol amines of alkyl branches and the Long carbon chain monohydric alcohol compounding of straight chain linear structure are used as physical property reinforcing agent in use, for containing
There is the physical property of the polyurethane insole of herb powder to promote effect more obvious.
Although above-described embodiment is described in detail technical solution of the present invention, technical side of the invention
Case is not limited to above embodiments, when not departing from thought and objective of the invention, to scope of the present invention patent
Equivalent change or modification made by content all should be technology scope of the invention.
Claims (15)
1. the polyurethane stock solution containing herb powder, characterized by comprising:
Polyol-mixture component A containing physical property reinforcing agent；
Isocyanate prepolymers body component B and
Herb powder C；
The physical property reinforcing agent is one or more of glycol amines or Long carbon chain monohydric alcohol of the branch containing chain alkyl.
2. the polyurethane stock solution according to claim 1 containing herb powder, which is characterized in that the physical property reinforcing agent
For the glycol amines of the branch containing chain alkyl and the mixture of Long carbon chain monohydric alcohol, mass ratio is 1:9~9:1.
3. the polyurethane stock solution according to claim 2 containing herb powder, which is characterized in that the branch containing chain alkyl
The glycol amines of chain are N- alkyl diethanol amine；
The skeleton symbol of the N- alkyl diethanol amine are as follows:
N=12,14,16,18.
4. the polyurethane stock solution according to claim 3 containing herb powder, which is characterized in that the Long carbon chain monohydric alcohol
For one or more of lauryl alcohol, tetradecyl alchohol, hexadecanol and octadecyl alcolol.
5. the polyurethane stock solution according to claim 4 containing herb powder, which is characterized in that the Long carbon chain monohydric alcohol
For one or more of the lauryl alcohol of straight chain linear structure, tetradecyl alchohol, hexadecanol and octadecyl alcolol.
6. the polyurethane stock solution according to claim 1 containing herb powder, which is characterized in that the herb powder C's
Additive amount is 5wt%~20wt% of the polyol-mixture component A gross mass, and the dosage of the physical property reinforcing agent is more
The 0.5wt%-7.0wt% of first alcohol mixture component A gross mass.
7. the polyurethane stock solution according to claim 6 containing herb powder, which is characterized in that contain physical property reinforcing agent
The mass ratio of polyol-mixture component A and Isocyanate prepolymers body component B is 10:7~5:6.
8. according to the polyurethane stock solution described in claim 1 containing herb powder, which is characterized in that the herb powder C is mulberry
Leaf, feverfew, Prunella vulgaris, radix scutellariae, Yellow Fructus Gardeniae, late silkworm excrement, the root bark of tree peony, the root of Dahurain angelica, dried peppermint leaf, cassia seed, radix cyathulae, alum, Siberian cocklebur
One of son, Flos Magnoliae Liliflorae, dried orange peel, Pogostemon cablin, perilla leaf, honeysuckle, Flos Albiziae or honeysuckle or a variety of powder.
9. described in any item polyurethane stock solutions containing herb powder according to claim 1~8, which is characterized in that described to contain
There is the polyol-mixture component A of physical property reinforcing agent, the component including following mass percentage:
In the Isocyanate prepolymers body component B, the mass percentage of each raw material are as follows:
MDI-100 40%~58%
Carbodiimide-Modified MDI 2%~10%
Polyether polyol 40%~50%.
10. the polyurethane stock solution according to claim 9 containing herb powder, which is characterized in that the isocyanates is pre-
It also include phosphoric acid in interpolymer component B, the 0.0020wt% that the additional amount of the phosphoric acid is Isocyanate prepolymers body component B~
0.0060wt%.
11. the polyurethane stock solution according to claim 9 containing herb powder, which is characterized in that the polyether polyols
Alcohol is with one or more of ethylene glycol, diglycol or glycerine for initiator, by 1,2- propylene oxide ring-opening polymerisation
Or propylene oxide is copolymerized to obtain with ethylene oxide, degree of functionality is 2~3, and number-average molecular weight is 2000~7000, preferably polyethers
Polyalcohol 330N, polyether polyol 360N, polyether polyol TED-28, polyether polyol KE-810 or polyether polyol KE-804
One or more of.
The chain extender is ethylene glycol, 1,4-butanediol, diglycol, 1,3-PD, dipropylene glycol, two contractings three
One or more of ethylene glycol, tripropylene glycol；
The foaming agent is water；
The foam stabilizer is organic silicon surfactant；
The catalyst is the ethylene glycol solution that mass concentration is 33% triethylene diamine, one in bis- (dimethylaminoethyl) ethers
Kind or two kinds of mixtures；
The pore-creating agent be one of polypropylene oxide-ethylene oxide copolyether, polyoxygenated alkene-polysiloxane copolymer with
On；
The MDI-100 isocyanates is 4,4 ' -99% or more methyl diphenylene diisocyanate contents；
The Carbodiimide-Modified MDI is carbodiimide modified diphenylmethane diisocyanate.
12. the preparation method of described in any item polyurethane stock solutions containing herb powder according to claim 1~11, feature
It is, includes the following steps:
(1) by polyether polyol, chain extender, physical property reinforcing agent, foaming agent, foam stabilizer, catalyst, pore-creating agent in lower mixing, out
Material is sealed, and it is spare to obtain the polyol-mixture component A containing physical property reinforcing agent；
(2) it is spare to weigh herb powder C；
(3) MDI-100, Carbodiimide-Modified MDI, phosphoric acid, polyether polyol are reacted, obtains the Isocyanate prepolymers
Body component B is spare.
13. the application of described in any item polyurethane stock solutions containing herb powder, feature exist according to claim 1~11
In being used to prepare the Chinese medicine health-care polyurethane insole of high physical property.
14. application according to claim 13, which is characterized in that application method is as follows: the herb powder C is added
It is mixed in polyol-mixture component A containing physical property reinforcing agent, obtains and contain the more of physical property reinforcing agent containing herb powder C
First alcohol mixture component A, and maintain its temperature at 20~30 DEG C；The temperature of Isocyanate prepolymers body component B is 20~30 DEG C；It will
The two components mixing that above-mentioned steps obtain, injection temperature are reaction 4~6min molding in 40~50 DEG C of molds, demoulding, curing 45
~50h obtains the Chinese medicine health-care polyurethane insole of high physical property.
15. the preparation method of described in any item polyurethane stock solutions containing herb powder according to claim 1~11, feature
It is, includes the following steps: that the polyol-mixture component containing physical property reinforcing agent for the herb powder C is added, i.e.,
Polyurethane stock solution containing herb powder includes polyol-mixture component and isocyanide containing physical property reinforcing agent and herb powder
Acid esters performed polymer component.
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