CN106560480A - Formula and preparation method of high-fluidity degradable polyurethane shoe material - Google Patents

Formula and preparation method of high-fluidity degradable polyurethane shoe material Download PDF

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Publication number
CN106560480A
CN106560480A CN201610626615.4A CN201610626615A CN106560480A CN 106560480 A CN106560480 A CN 106560480A CN 201610626615 A CN201610626615 A CN 201610626615A CN 106560480 A CN106560480 A CN 106560480A
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Prior art keywords
component
formula
footwear material
degradable
high fluidity
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李红领
廖志勇
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COLORTECH (GUANGZHOU) CHEMICALS Co Ltd
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COLORTECH (GUANGZHOU) CHEMICALS Co Ltd
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Priority to CN201610626615.4A priority Critical patent/CN106560480A/en
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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
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/6696—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B1/00—Footwear characterised by the material
    • A43B1/10—Footwear characterised by the material made of rubber
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B1/00—Footwear characterised by the material
    • A43B1/14—Footwear characterised by the material made of plastics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
    • B29C39/02—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
    • B29C39/22—Component parts, details or accessories; Auxiliary operations
    • B29C39/44—Measuring, controlling or regulating
    • 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
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/36—Hydroxylated esters of higher fatty acids
    • 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
    • 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
    • C08J9/12—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 physical blowing agent
    • C08J9/14—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 physical blowing agent organic
    • C08J9/141—Hydrocarbons
    • 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
    • C08J9/12—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 physical blowing agent
    • C08J9/14—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 physical blowing agent organic
    • C08J9/143—Halogen containing compounds
    • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
    • 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
    • C08J9/12—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 physical blowing agent
    • C08J9/14—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 physical blowing agent organic
    • C08J9/143—Halogen containing compounds
    • C08J9/147—Halogen containing compounds containing carbon and halogen atoms only
    • 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
    • C08G2101/00—Manufacture of cellular products
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
    • C08J2203/144—Perhalogenated saturated hydrocarbons, e.g. F3C-CF3
    • 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
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/08—Polyurethanes from polyethers

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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)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The present invention discloses a formula and a preparation method of a high-fluidity degradable polyurethane shoe material, wherein the used raw materials comprise a component A and a component B according to a ratio of the component A to the component B of 1:(0.8-1.2). The preparation process comprises: 1) weighing the component A according to the ratio by using a container, and uniformly mixing; 2) mixing the components A and B for 7-10 s at a stirring speed of 1000-3000 r/min, wherein the temperatures of the components A and B are maintained at 20-28 DEG C; 3) pouring the mixed components into a shoe material mold cavity having good sealing property, and aging for 3-20 min, wherein the temperature of the mold is 40-60 DEG C; 4) opening the mold to obtain a polyurethane shoe material; and 5) placing for 24-48 h to complete the aging. According to the present invention, the reaction injection molding process is used; due to low viscosity and good fluidity of the components in the formula, the material can rapidly flow to each position of the molds having complex body shapes, and the foaming molding can be performed at the appropriate speed so as to obtain the finished product having the good appearance; and the product is subjected to the one time molding, is partially degradable, and has the low cost.

Description

A kind of formula and preparation method of high fluidity degradable polyurethane footwear material
Technical field
The present invention relates to the formula and system of a kind of polyurethane footwear material, especially a kind of high fluidity degradable polyurethane footwear material Preparation Method.
Background technology
Polyurethane, english abbreviation are PU, the general designation containing the macromolecular compound for repeating carbamate groups on main chain, It is polymerized with binary or multicomponent isocyanate by binary or multi-hydroxy compound.Polyurethane is different according to application, have CPU, TPU, MPU etc. are referred to as.Its raw material can be divided into isocyanates, polyalcohols and auxiliary agent class.
Polyurethane elastomer variety of raw material is various, and formula is varied, and adjustable extent is big.Matched somebody with somebody by adjusting polyurethane The excellent properties such as high intensity, good toughness, wear-resisting, oil resistant can be obtained, it had not only had the high resiliency of rubber but also had had the firm of plastics Property, it is referred to as " abrasive rubber ".It is widely used in automobile, building, Aero-Space, Medical treatment device as which has excellent properties The multiple fields such as tool, sporting articles, become the synthetic material of great development prospect.Microporous polyurethane elastomer should in footwear material field With extensive, as which has the advantages that good shock-absorbing capacity, light weight, wear-resisting, anti-skidding, become a kind of important in shoemaking industry The sole of many footwear such as supplementary material, golf shoes, spike, football boot, skiing boots, sneakers, safety shoe, heel, footwear The important accessory such as head, shoe pad be all with made by polyurethane, it is not only elegant in appearance and comfortable durable.
Polyurethane footwear material can be obtained by reaction and injection molding process, and reaction injection molding moulds RIM also known as reaction injection molding(RIM) （Reaction Injection Moulding）, it is to be measured by the little material of molecular weight in liquid form, moment mixing While inject mould, and reacted in die cavity rapidly, material molecule amount is sharply increased, and production is containing new at a terrific speed The technique of the brand-new polymer of characteristic group structure.This technique processes simple and fast, low cost.
But improve along with people's living standard, for the requirement more and more higher of footwear material appearance property, this generally requires multiple Miscellaneous product could meet requirement, but the mould of complexity often brings to original technology and is difficult to one-time formed puzzlement, reason Be original technology formula material viscosity it is higher, mobility is poor, it is difficult to which quickly flowing to each position of complicated die causes Easily there is defect in products appearance.
The raw material of production polyurethane polyethers, polyester is by oil downstream product processing gained, the oil money in the whole world at present There is limitation by scarce today of being becoming tight, the conventional polyether polyols produced using PETROLEUM PROCESSING product in source.
Vegetable oil is by being modified, epoxidation, hydroxylating are obtained different hydroxyl values, the vegetable oil of degree of functionality, different viscosities is more First alcohol, the polyurethane by obtained in vegetable oil polyol have degradability, and vegetable oil China is the important production of vegetable oil State, with aboundresources, the low advantage of renewable and price.
In the prior art, for polyurethane RIM（Reaction injection molding）Technology, reply complicated die is except Design of Dies Upper improvement, is also exactly multiple injection molding, but the problem for existing is：In batches repeatedly material feeding often to reduce polyurethane product resistance to With property, while increasing cost of manufacture, while the viscosity of original technology formula material is higher, mobility is poor, it is difficult to quick to flow Products appearance is caused defect easily occur to each position of complicated die.
The content of the invention
For the deficiencies in the prior art, the invention provides a kind of new polyurethane footwear material formula, relative to general poly- ammonia Ester footwear material formula, it is main by from low viscous vegetable oil polyol petroleum replacing ethoxylated polyhydric alcohol in this formula, to reach drop Low viscosity increases the purpose of mobility, using reaction and injection molding process, the vegetable oil polyol in formula adding viscosity low Reducing material viscosity, quickly and evenly stream puts each corner of die cavity to all or part of petroleum replacing ethoxylated polyhydric alcohol to allow material, matches somebody with somebody Close the suitable gel expansion rate finished product good to obtain outward appearance.
The technical scheme is that：A kind of formula of high fluidity degradable polyurethane footwear material, it is characterised in that formula Including component A and B component, wherein B component is isocyanates semi-prepolymer, and component A is mixed by the component of following masses part：
30 ~ 80 parts of vegetable oil polyol, 0 ~ 70 part of oil polyether polyol
0 ~ 15 part of chain extension-crosslinking agent, 0 ~ 3 part of foam stabiliser
0.5 ~ 8 part of catalyst, 0.1 ~ 2 part of water
0 ~ 15 part of foaming agent
A：The amount ratio of B is 1:（0.8~1.2）；The vegetable oil polyol is the one kind by obtained by plant oil modified and hydroxylating Polyhydric alcohol is specially low viscous soybean oil polyol or castor oil polyhydric alcohol, Petiolus Trachycarpi oil polyalcohol, it is polynary to reclaim vegetable oil One or more of alcohol, and viscosity is less than 500cps（25℃）, in component A, vegetable oil polyol mass content is higher, and system is glued Degree is lower；The vegetable oil polyol parameter of materials：
Hydroxyl value 100 ~ 300mgKOH/g, 150 ~ 250cps of viscosity（25℃）
0.9 ~ 1.2g/cm of density degrees of functionality 3 ~ 8
Molecular weight 1500 ~ 3000.
The oil polyether polyol is to be gathered by the small molecule polyols such as glycerol and/or Propylene Glycol and open loop of epoxy compound Close the reactant of gained.
The chain extension-crosslinking agent be ethylene glycol and diglycol, glycerol, diethanolamine, 2- methyl-（1,3）- the third two One or more of alcohol.
The catalyst is triethylenediamine, 33% propylene glycol solution and double（Dimethylaminoethyl）Ether, tin dilaurate two One or more of butyl tin, double morpholine Anaesthetie Ethers.
The foam stabiliser is organic silicon surfactant.
The foaming agent is one or more of a fluorine dichloroethanes and Pentamethylene., fluoro trichloromethane.
A kind of preparation method of high fluidity degradable polyurethane footwear material, it is characterised in that its preparation process includes as follows Step：
1）With container by component A by mix homogeneously after proportioning weighing；
2）A, B component are mixed 7 ~ 10 seconds under the mixing speed of 1000-3000 r/min, A, B component temperature be maintained at 20 ~ 28℃；
3）Pour the die cavity of footwear material good seal after A, B component mixing into（Mould as needed can be with aerofluxuss）, mold temperature 40 ~ 60 DEG C, ripening 3 ~ 20 minutes；
4）Open mould and obtain polyurethane footwear material；
5）Placement completes ripening in 24 ~ 48 hours.
The present invention reaction mechanism be：
The reaction of isocyanates and OH
RNCO+R′OH →RNHCOOR′
The reaction of isocyanates and water
2RNCO+ H2O → RNHCONHR + CO2↑
Beneficial effects of the present invention are：The present invention adopts reaction and injection molding process, relative to general footwear material formula, the present invention Formula due to viscosity it is low, good fluidity, the mould complicated for some type bodies, material can quickly flow to each position of mould Put, then with appropriate speed foaming, obtain the good finished product of outward appearance；And the formula one-shot forming, part degradable, Low cost.
Specific embodiment
Below the specific embodiment of the present invention is described further：
Embodiment 1：
On a production line, two component of A, B is cast in footwear material mould cavity by casting machine, after ripening, obtains low resilience footwear Material.
The B component be isocyanates, component A stirred by following weight item after gained：
50 parts of vegetable oil polyol, 40 parts of oil polyether polyol
5 parts of chain extension-crosslinking agent, 1 part of foam stabiliser
4 parts of catalyst, 1 part of water
6 parts of foaming agent
The consumption of A, B（Quality）Than for A：B=1:0.8~1.2.
Wherein, vegetable oil polyol is a kind of polyhydric alcohol by obtained by plant oil modified and hydroxylating, specially low viscosity One or more of soybean oil polyol or castor oil polyhydric alcohol, Petiolus Trachycarpi oil polyalcohol, recovery vegetable oil polyol, vegetable oil is more First alcohol viscosity is less than 500cps（25℃）, in component A, vegetable oil polyol mass content is higher, and system viscosity is lower, vegetable oil Polyol mass parameter：
Hydroxyl value 100 ~ 300mgKOH/g, 150 ~ 250cps of viscosity（25℃）
0.9 ~ 1.2g/cm of density degrees of functionality 3 ~ 8
Molecular weight 1500 ~ 3000
Wherein, oil polyether polyol is obtained by the small molecule polyols such as glycerol, Propylene Glycol are polymerized with open loop of epoxy compound One or more.Chain extension-crosslinking agent be ethylene glycol and diglycol, glycerol, diethanolamine, 2- methyl-（1,3）- the third two One or more of alcohol.Catalyst is triethylenediamine, 33% propylene glycol solution and double（Dimethylaminoethyl）Ether, two Laurels One or more of sour dibutyl tin, double morpholine Anaesthetie Ethers.Foam stabiliser is organic silicon surfactant.Foaming agent is one One or more of fluorine dichloroethanes and Pentamethylene., fluoro trichloromethane.
Embodiment 2：
Component A stirred by following weight item after gained：
30 parts of vegetable oil polyol, 60 parts of oil polyether polyol
7 parts of chain extension-crosslinking agent, 0.6 part of foam stabiliser
3 parts of catalyst, 1 part of water
8 parts of foaming agent
Remaining is with embodiment 1
Embodiment 3：
Component A stirred by following weight item after gained：
70 parts of vegetable oil polyol, 20 parts of oil polyether polyol
3 parts of chain extension-crosslinking agent, 1 part of foam stabiliser
5 parts of catalyst, 0.5 part of water
9 parts of foaming agent
Remaining is with embodiment 1
The present invention by using polyurethane foam moulding process, for some complicated moulds can reduce the defect of molded body, So as to obtain a kind of high fluidity degradable polyurethane footwear material product of more high-quality.
Merely illustrating the principles of the invention described in above-described embodiment and description and most preferred embodiment, without departing from this On the premise of spirit and scope, the present invention also has various changes and modifications, and these changes and improvements both fall within requirement and protect In the scope of the invention of shield.

Claims (7)

1. a kind of formula of high fluidity degradable polyurethane footwear material, it is characterised in that formula includes component A and B component, wherein B component is isocyanates semi-prepolymer, and component A mixed by the component of following masses part：
30 ~ 80 parts of vegetable oil polyol, 0 ~ 70 part of oil polyether polyol
0 ~ 15 part of chain extension-crosslinking agent, 0 ~ 3 part of foam stabiliser
0.5 ~ 8 part of catalyst, 0.1 ~ 2 part of water
0 ~ 15 part of foaming agent
A：The amount ratio of B is 1:（0.8~1.2）；The vegetable oil polyol is that low viscous soybean oil polyol or Oleum Ricini are more One or more of first alcohol, Petiolus Trachycarpi oil polyalcohol, recovery vegetable oil polyol, and viscosity is less than 500cps（25℃）, the plant Thing oil polyalcohol parameter of materials：
Hydroxyl value 100 ~ 300mgKOH/g, 150 ~ 250cps of viscosity（25℃）
0.9 ~ 1.2g/cm of density degrees of functionality 3 ~ 8
Molecular weight 1500 ~ 3000.
2. the formula of high fluidity degradable polyurethane footwear material according to claim 1, it is characterised in that：The oil gathers Ethoxylated polyhydric alcohol is the reactant obtained by glycerol and/or Propylene Glycol are polymerized with open loop of epoxy compound.
3. the formula of degradable low resilience footwear material according to claim 1, it is characterised in that：The chain extension-crosslinking agent is second Glycol and diglycol, glycerol, diethanolamine, 2- methyl-（1,3）One or more of-Propylene Glycol.
4. the formula of high fluidity degradable polyurethane footwear material according to claim 1, it is characterised in that：The catalyst For triethylenediamine, 33% propylene glycol solution and double（Dimethylaminoethyl）Ether, dibutyl tin laurate, double morpholine diethyls One or more of base ether.
5. the formula of high fluidity degradable polyurethane footwear material according to claim 1, it is characterised in that：The foam is steady Agent is determined for organic silicon surfactant.
6. the formula of high fluidity degradable polyurethane footwear material according to claim 1, it is characterised in that：The foaming agent One or more for a fluorine dichloroethanes and Pentamethylene., fluoro trichloromethane.
7. the preparation method of high fluidity degradable polyurethane footwear material according to claim 1, it is characterised in that its preparation Process comprises the steps：
1）With container by component A by mix homogeneously after proportioning weighing；
2）A, B component are mixed 7 ~ 10 seconds under the mixing speed of 1000-3000 r/min, A, B component temperature be maintained at 20 ~ 28℃；
3）Pour the die cavity of footwear material good seal, 40 ~ 60 DEG C of mold temperature, ripening 3 ~ 20 minutes after A, B component mixing into；
4）Open mould and obtain polyurethane footwear material；
5）Placement completes ripening in 24 ~ 48 hours.
CN201610626615.4A 2016-08-03 2016-08-03 Formula and preparation method of high-fluidity degradable polyurethane shoe material Pending CN106560480A (en)

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CN113248679A (en) * 2020-07-02 2021-08-13 王聪 Novel non-Newtonian polyurethane energy-absorbing buffer material and method for manufacturing insole by using same

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Application publication date: 20170412