CN106560479A - Manufacturing technique of using soybean oil-based polyhydric alcohols to prepare polyurethane shoe material - Google Patents
Manufacturing technique of using soybean oil-based polyhydric alcohols to prepare polyurethane shoe material Download PDFInfo
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- CN106560479A CN106560479A CN201610626614.XA CN201610626614A CN106560479A CN 106560479 A CN106560479 A CN 106560479A CN 201610626614 A CN201610626614 A CN 201610626614A CN 106560479 A CN106560479 A CN 106560479A
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- soybean oil
- polyurethane
- footwear material
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D35/00—Producing footwear
- B29D35/12—Producing parts thereof, e.g. soles, heels, uppers, by a moulding technique
-
- 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
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
-
- 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2230/00—Compositions for preparing biodegradable polymers
-
- 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)
- Mechanical Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a manufacturing technique of using soybean oil-based polyhydric alcohols to prepare a polyurethane shoe material. The raw materials adopted by the manufacturing technique comprise a component A and a component B, and a dosage ratio of the component A and the component B is (0.8-1.2). A preparing process comprises the steps of 1, using a vessel to weigh the component A according to a ratio, and afterwards, uniformly mixing the component A; 2, mixing the component A and the component B at the stirring speed of 1000-3000 r/min for 7-10 seconds, and maintaining the temperatures of the component A and the component B at 20-28 DEG C; 3, pouring the component A and the component B into a shoe material die with good sealing after mixing the component A and the component B, maintaining the temperature of the die at 40-60 DEG C, and conducting curing for 3-30 minutes; 4, opening the die to obtain the polyurethane shoe material with slow springback; 5, still standing the polyurethane for 48 hours to accomplish the curing. According to the manufacturing technique of using the soybean oil-based polyhydric alcohols to prepare the polyurethane shoe material, soybean oil polygydric alcohols with a high degree of functionality and a proper hydroxyl valve are added in a formula to completely or partially replace petroleum ether polyhydric alcohols, and a proper chain extension cross-linking agent and isocyanate are also added to form a spatial network structure with higher crosslinking density, an inhibiting phase is separated, and so that a slow springback effect is achieved.
Description
Technical field
The present invention relates to a kind of polyurethane footwear material, especially a kind of utilization soybean oil base polyol prepare polyurethane footwear material
Production technology.
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 and (catalyst, crosslinking chain extender, send out
Infusion, filler, coloring agent etc.).
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.
Low resilience, that is, it has often been said that memory foam (Memory Foam), be a kind of with open cell design
Polyurethane high molecule polymer, the material have a special viscous-elastic behaviour, embody very soft material behavior, and have very strong punching
Hitting can absorbability.This material molecule is very sensitive to temperature, so being also called warming memory foam.There are too many research and application
Example shows, it is protection health and skin be affine, comfort etc. aspect of performance exceeds well over other materials.Exploitation
Medicated pillow, mattress, back cushion, sofa etc. low resilience product it to numerous users with it is fine experience while, bringing many has
The health help of benefit, while low resilience is applied in footwear material, adapts to human body foot type, makes the gravity of people be able to contact in whole foot
Dispersion on face gives good comfort.
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.
Slow-rebound foaming material prescription prepared by conventional petroleum polyether polyol has adjustable extent narrow, is also easy to produce closed pore, leads
The shortcomings of causing shrink of product, needs to make cell collapse perforate by adding tapping machine or roll process.
Production polyurethane polyethers, the raw material of polyester process gained by oil downstream product at present in addition, in whole world stone
There is limitation by scarce today of being becoming tight, the conventional polyether polyols produced using PETROLEUM PROCESSING product in oily resource.
In the prior art, polyurethane mainly manufactures slow rebound polyurethane using oil ethoxylated polyhydric alcohol when midsole is prepared
Footwear material, but exist problem be：With respect to vegetable oil polyol, oil ethoxylated polyhydric alcohol high cost, resource are non-renewable, can not drop
Solution, and slow-rebound foaming material prescription adjustable extent prepared by conventional petroleum polyether polyol is narrow, is also easy to produce closed pore, causes product
The shortcomings of contraction.
The content of the invention
For the deficiencies in the prior art, the present invention is prepared and has slow returning by being used as raw material using soybean oil polyol
The polyurethane footwear material product of elastic energy；Soybean oil is obtained different hydroxyl values, degree of functionality, difference by modified, epoxidation, hydroxylating
The soybean oil polyol of viscosity, in the whole world, by scarce today of being becoming tight, vegetable oil cheap and easy to get can as one kind for petroleum resources
Regenerated resources are just being increasingly subject to the concern of people.Soybean oil polyol derives from Renewable resource Semen sojae atricolor, and its degree of functionality is higher,
Low price, polymerization product have degradability, manufacture low resilience footwear material using soybean oil polyol, with percent opening height, resource
The low advantage of abundant, renewable, price.
The technical scheme is that：A kind of utilization soybean oil base polyol prepares the formula of polyurethane footwear material, its feature
It is that formula includes component A and B component, wherein B component is isocyanates semi-prepolymer, component of the component A by following masses part
Mix：
30 ~ 100 parts of soybean oil polyol, 0 ~ 70 part of oil polyether polyol
0 ~ 10 part of chain extension-crosslinking agent, 0 ~ 2 part of foam stabiliser
0.1 ~ 5 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）；Wherein, the soybean oil polyol is by obtained by soybean oil modified and hydroxylating
And a kind of higher polyhydric alcohol of degree of functionality, its physics, chemical parameters：
Hydroxyl value 100 ~ 500mgKOH/g, 100 ~ 3000cps of viscosity（25℃）
0.9 ~ 1.2g/cm of density degrees of functionality 4 ~ 8
Molecular weight 200 ~ 4000.
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 soybean oil base polyol prepares the production technology of polyurethane footwear material, it is characterised in that its preparation process includes
Following 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 1000-3000r/min, A, B component temperature are maintained at 20 ~ 28
℃；
3）Pour the mould 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 ~ 30 minutes；
4）Open mould and obtain slow rebound polyurethane footwear material；
5）Ripening is completed after placing 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：
1st, soybean oil polyol degree of functionality is high, prepare the easy perforate of polyurethane, price are low, degradable, using reaction injection molding
Technique, adds degree of functionality high in formula, the suitable soybean oil polyol all or part petroleum replacing ethoxylated polyhydric alcohol of hydroxyl value and
Appropriate chain extension-crosslinking agent forms the higher spacial framework of crosslink density with isocyanates, suppresses to be separated, so as to reach
Low resilience effect；The present invention can improve polyurethane industries among others by petroleum resources and petroleum resources problem in short supply；Soybean oil is polynary
Alcohol belongs to degradable resource, can improve the current pollution problem of polyurethane industries among others, and reduce production cost, improve competitiveness in row.
2nd, the reaction and injection molding process that the present invention is adopted, footwear material polyether polyol viscosity is typically in 700 ~ 1000cps
（25℃）Left and right, PEPA viscosity is higher, and 200 cps of vegetable oil polyol viscosity（25℃）Left and right, by part or
Replacing whole oil ethoxylated polyhydric alcohol can prepare the low resilience footwear material that physical property is good, percent opening is high, formula hardness, the thing
Rationality be able to can be adjusted as needed, 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：
45 parts of soybean oil polyol, 50 parts of oil polyether polyol
5 parts of chain extension-crosslinking agent, 0.5 part of foam stabiliser
3 parts of catalyst, 1 part of water
5 parts of foaming agent
The consumption of A, B（Quality）Than for A：B=1:0.8~1.2.
Wherein, soybean oil polyol be by soybean oil modified and obtained by hydroxylating and a kind of higher polyhydric alcohol of degree of functionality,
Its physics, chemical parameters：
Hydroxyl value 100 ~ 500mgKOH/g, 100 ~ 3000cps of viscosity（25℃）
0.9 ~ 1.2g/cm of density degrees of functionality 4 ~ 8
Molecular weight 200 ~ 4000.
Wherein, oil polyether polyol is to be polymerized with open loop of epoxy compound by small molecule polyols such as glycerol, Propylene Glycol
One or more of gained.Chain extension-crosslinking agent be ethylene glycol and diglycol, glycerol, diethanolamine, 2- methyl-（1,3）-
One or more of Propylene Glycol.Catalyst is 33% propylene glycol solution of triethylenediamine and double（Dimethylaminoethyl）Ether, February
One or more of dilaurylate, double morpholine Anaesthetie Ethers.Foam stabiliser is organic silicon surfactant.Foaming agent is
One or more of one fluorine dichloroethanes and Pentamethylene., fluoro trichloromethane.
Embodiment 2：
Component A stirred by following weight item after gained：
35 parts of soybean oil polyol, 60 parts of oil polyether polyol
7 parts of chain extension-crosslinking agent, 0.6 part of foam stabiliser
2.5 parts of catalyst, 1 part of water
7 parts of foaming agent
Remaining is with embodiment 1
Embodiment 3：
Component A stirred by following weight item after gained：
65 parts of soybean oil polyol, 25 parts of oil polyether polyol
3 parts of chain extension-crosslinking agent, 0.5 part of foam stabiliser
4 parts of catalyst, 0.5 part of water
8 parts of foaming agent
Remaining is with embodiment 1
The present invention low resilience urethane foam resilient foam be characterized in that rebound velocity is slower, resilience is related to the form result of polyurethane, hard section and
The phase separation degree of soft section is lower, and resilience is lower.Herein using the higher soybean oil polyol of degree of functionality, hydroxyl value and suitably
Chain extension-crosslinking agent and isocyanates form the higher spacial framework of crosslink density, suppress to be separated, so as to reach slow returning
Play effect.
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 utilization soybean oil base polyol prepares the formula of polyurethane footwear material, it is characterised in that formula includes component A and B
Component, wherein B component are isocyanates semi-prepolymer, and component A mixed by the component of following masses part：
30 ~ 100 parts of soybean oil polyol, 0 ~ 70 part of oil polyether polyol
0 ~ 10 part of chain extension-crosslinking agent, 0 ~ 2 part of foam stabiliser
0.1 ~ 5 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）；Wherein, the soybean oil polyol is by obtained by soybean oil modified and hydroxylating
And a kind of higher polyhydric alcohol of degree of functionality, its physics, chemical parameters：
Hydroxyl value 100 ~ 500mgKOH/g, 100 ~ 3000cps of viscosity（25℃）
0.9 ~ 1.2g/cm of density degrees of functionality 4 ~ 8
Molecular weight 200 ~ 4000.
2. utilization soybean oil base polyol according to claim 1 prepares the formula of polyurethane footwear material, it is characterised in that：Institute
It is the reactant obtained by glycerol and/or Propylene Glycol are polymerized with open loop of epoxy compound to state oil polyether polyol.
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. utilization soybean oil base polyol according to claim 1 prepares the formula of polyurethane footwear material, it is characterised in that：Institute
Catalyst is stated for triethylenediamine, 33% propylene glycol solution and double（Dimethylaminoethyl）It is ether, dibutyl tin laurate, double
One or more of morpholine Anaesthetie Ether.
5. utilization soybean oil base polyol according to claim 1 prepares the formula of polyurethane footwear material, it is characterised in that：Institute
Foam stabiliser is stated for organic silicon surfactant.
6. utilization soybean oil base polyol according to claim 1 prepares the formula of polyurethane footwear material, it is characterised in that：Institute
State one or more that foaming agent is a fluorine dichloroethanes and Pentamethylene., fluoro trichloromethane.
7. utilization soybean oil base polyol according to claim 1 prepares the production technology of polyurethane footwear material, and its feature exists
In 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 1000-3000r/min, A, B component temperature are maintained at 20 ~ 28
℃；
3）Pour the mould of footwear material good seal, 40 ~ 60 DEG C of mold temperature, ripening 3 ~ 30 minutes after A, B component mixing into；
4）Open mould and obtain slow rebound polyurethane footwear material；
5）Ripening is completed after placing 48 hours.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610626614.XA CN106560479A (en) | 2016-08-03 | 2016-08-03 | Manufacturing technique of using soybean oil-based polyhydric alcohols to prepare polyurethane shoe material |
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| CN201610626614.XA CN106560479A (en) | 2016-08-03 | 2016-08-03 | Manufacturing technique of using soybean oil-based polyhydric alcohols to prepare polyurethane shoe material |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108164677A (en) * | 2018-01-23 | 2018-06-15 | 广州市聚科聚氨酯有限公司 | Soybean oil polyol prepares and its application in polyurethane foam |
| CN110229303A (en) * | 2019-06-26 | 2019-09-13 | 吉林大学 | A kind of automobile-used polyurethane sound absorption material and preparation method thereof based on soybean oil polyol |
| CN111454426A (en) * | 2020-04-25 | 2020-07-28 | 泉州西米露新材料科技有限公司 | Environment-friendly degradable aromatic polyurethane foam material and preparation method thereof |
| CN113087870A (en) * | 2021-03-01 | 2021-07-09 | 辽宁石油化工大学 | Preparation method of soybean oil-based polyurethane foam based on different structures |
| CN117223934A (en) * | 2023-09-15 | 2023-12-15 | 东莞市森宏新材料科技有限公司 | Organic nanometer environment-friendly sole and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108164677A (en) * | 2018-01-23 | 2018-06-15 | 广州市聚科聚氨酯有限公司 | Soybean oil polyol prepares and its application in polyurethane foam |
| CN110229303A (en) * | 2019-06-26 | 2019-09-13 | 吉林大学 | A kind of automobile-used polyurethane sound absorption material and preparation method thereof based on soybean oil polyol |
| CN111454426A (en) * | 2020-04-25 | 2020-07-28 | 泉州西米露新材料科技有限公司 | Environment-friendly degradable aromatic polyurethane foam material and preparation method thereof |
| CN113087870A (en) * | 2021-03-01 | 2021-07-09 | 辽宁石油化工大学 | Preparation method of soybean oil-based polyurethane foam based on different structures |
| CN117223934A (en) * | 2023-09-15 | 2023-12-15 | 东莞市森宏新材料科技有限公司 | Organic nanometer environment-friendly sole and preparation method thereof |
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Application publication date: 20170412 |