CN108219108A - A kind of hydrolysis resistant polyurethane sole and preparation method thereof - Google Patents
A kind of hydrolysis resistant polyurethane sole and preparation method thereof Download PDFInfo
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- CN108219108A CN108219108A CN201711437280.2A CN201711437280A CN108219108A CN 108219108 A CN108219108 A CN 108219108A CN 201711437280 A CN201711437280 A CN 201711437280A CN 108219108 A CN108219108 A CN 108219108A
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- 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
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
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- C08G18/30—Low-molecular-weight compounds
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- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
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Abstract
The invention discloses a kind of hydrolysis resistant polyurethane soles and preparation method thereof, are related to material for sole of shoe technical field.Wherein polyurethane shoe-sole includes component A and B component, and component A includes the component of following parts by weight：40 60 parts of polyether polyol；30 50 parts of polyester polyol；12 parts of non-metallic catalyst；15 parts of chain extender；12 parts of foam stabilizer；12 parts of water；B component includes the component of following parts by weight：20 40 parts of isocyanates；10 30 parts of polyethylene glycol adipate.The present invention introduces polyether polyol in polyurethane shoe-sole, simultaneously using non-metallic catalyst, it avoids introducing metal ion, adds metal-chelator and remove impurity metal ion, add isothiazolinone and inhibit or kill the microorganism that polyurethane shoe-sole can be caused to degrade, isocyanates with phenyl ring improves the crystallinity of polyurethane, so that diffusion of moisture speed slows down, five cooperate, synergistic, the anti-hydrolytic performance of polyurethane shoe-sole is improved, extends its service life in wet environment.
Description
Technical field
The present invention relates to material for sole of shoe technical field, more specifically, it relates to a kind of hydrolysis resistant polyurethane sole and its
Preparation method.
Background technology
Polyurethane belongs to high-tech, high-performance, high value-added product, has as novel and multifunctional high molecular material
Superior physical mechanical property, acid-alkali-corrosive-resisting performance, the advantages that high-mechanic performance and hardness range is wide, in material industry
In occupy an important position, have become one of the mainstay material in sole market at present, the application on Labor protection shoes is also relatively broad.
The defects of polyester polyurethane is maximum is that anti-hydrolytic performance is poor, in use, easily degrading and shortening and use in wet environment
Service life causes waste of material and huge economic loss.
A kind of thermoplastic polyurethane elastomer is disclosed in the Chinese invention patent of Publication No. CN103073697A
Processing technology includes the following steps：The predry of polyethylene glycol adipate, methyl diphenylene diisocyanate and 1,4- butanediols
It is dry；The first of raw material mixes, wherein adding in the Carbodiimides hydrolysis agent of 0.1-10wt%；Substance after just mixed from pouring head into
Enter in double screw rod extruder, reaction temperature is 140-250 DEG C, pressure 4-7MPa, and the temperature control of machine barrel is at least
It is divided into four sections；After the completion of reaction, by head extrusion adhesive tape, through underwater tie rod pelletizing and and dehydration obtain product particles；Then again
It is dry.
In order to improve the anti-hydrolytic performance of polyurethane material in above-mentioned patent, it is added to hydrolysis agent, but hydrolysis agent
The surface layer of polyurethane can be moved to, the hydrolytic resistance of polyurethane material is caused to decline, it is, therefore, desirable to provide a kind of new scheme is come
It solves the above problems.
Invention content
In view of the deficienciess of the prior art, the purpose of the present invention one is to provide a kind of hydrolysis resistant polyurethane sole, lead to
It crosses the metal ion removed in polyurethane shoe-sole, add in the preferable aromatic rings class raw material of water-resistance and preservative, solve poly- ammonia
The problem of ester sole hydrolytic resistance is poor has the advantages that hydrolytic resistance is good.
To achieve the above object one, the present invention provides following technical solutions：
A kind of hydrolysis resistant polyurethane sole, including component A and B component, component A includes the component of following parts by weight：
40-60 parts of polyether polyol；
30-50 parts of polyester polyol；
1-2 parts of non-metallic catalyst；
1-5 parts of chain extender；
1-2 parts of foam stabilizer；
1-2 parts of water；
B component includes the component of following parts by weight：
20-40 parts of isocyanates；
10-30 parts of polyethylene glycol adipate.
Through the above technical solutions, by introducing polyether polyol in polyurethane shoe-sole, the ether official in polyether polyol
The shortcomings that rolling into a ball with preferable anti-hydrolytic performance, overcome polyester-type；Since flexible polyurethane is easily hydrolyzed into molecular weight
Relatively low product, in the presence of having alkali and certain metal ion catalysts, this hydrolysis can occur rapidly, therefore,
The present invention is avoided introducing the metal ion that can hydrolyze polyurethane, is improved the resistance to of polyurethane shoe-sole using non-metallic catalyst
Hydrolysis property.
Further, the hydrolysis resistant polyurethane sole further includes 0.1-0.5 parts of metal-chelators.
Through the above technical solutions, due to inevitably introducing a small amount of metal ion in process of production, and this
A little metal ions can cause polyurethane shoe-sole to hydrolyze, will be in metal ion inclusion to chelating agent by adding in metal-chelator
Portion becomes stable, molecular weight bigger compound, so as to further improve the anti-hydrolytic performance of polyurethane shoe-sole.
Further, the metal-chelator includes aminotrimethylenephosphonic acid, ethylene diamine tetra methylene phosphonic acid, amino front three
Pitch any one in phosphonic acids.
Through the above technical solutions, above-mentioned chelating agent belongs to type of organophosphonic acides quasi-chelate compound, have preferably to Ca, Mg salt
Chelation.
Further, the hydrolysis resistant polyurethane sole further includes 0.5-2.5 parts of isothiazolinone.
Through the above technical solutions, since there are ester bond, the microorganism (such as mould) in nature passes through in polyurethane
Attack ester bond can cause degradation of polyurethane, and this bacterial degradation is more rapider than being hydrolyzed caused by metal ion；In formula
Polyethers also is able to hinder the close of mould, and microorganism can be inhibited or kill by adding in preservative isothiazolinone, avoid microorganism
Polyurethane shoe-sole is caused to be degraded.
Further, the polyether polyol includes polyoxypropyleneglycol, polyethylene glycol oxide copolymerization ethoxylated polyhydric alcohol, poly- four
Any one in hydrogen furan polyols.
Through the above technical solutions, the ether functional group in polyether polyol has preferable anti-hydrolytic performance, compensate for poly-
The shortcomings that ester type, improves the anti-hydrolytic performance of polyurethane shoe-sole.
Further, the polyester polyol includes poly- sebacic acid-polybutadiene binary alcohol esters polyalcohol, polyethylene glycol two
Any one in ethylene glycol sebacic acid ester polyol, polyadipate ethylene glycol diethylene glycol glycerine ester polyol.
Through the above technical solutions, the property of dihydric alcohol affects the hydrolytic resistance of polyurethane, above-mentioned polyester polyol
With longer methene chain, hydrogen chain ratio is reduced, improves hydrophobicity, reduces the infiltration of water, so as to improve polyurethane shoe-sole
Anti-hydrolytic performance.
Further, the non-metallic catalyst includes morpholine, N, any one in N dimethyl cyclohexylamine, triethanolamine
Kind.
Through the above technical solutions, non-metallic catalyst not only increases reaction speed, and avoid introducing metal ion.
Further, the chain extender includes any one in ethylene glycol, methyl propanediol, glycerine；The foam stabilizer
For dimethyl siloxane or polyether silicone.
Through the above technical solutions, chain extender reduces the copolymerization of formation by making the free radical in growth that chain tra nsfer occur
The molecular weight of object, thus reducing influences between the viscosity of polymer polyatomic alcohol and dispersion stabilization and the polymer molecule of filterability
Crosslinked action；Pore-forming is uniform when foam stabilizer causes polyurethane foam, and structural integrity is strong.
Further, the isocyanates include methyl diphenylene diisocyanate, two cyclohexyl methane diisocyanates,
Any one in naphthalene diisocyanate.
Through the above technical solutions, purely linear polyurethane is influenced by its low-crystallinity, it is higher in amorphous area
Region moisture is easily accessible polyurethane, and attack macromolecular chain causes to hydrolyze, and the isocyanates with phenyl ring improves the knot of polyurethane
Brilliant degree so that diffusion of moisture speed slows down, so as to improve the anti-hydrolytic performance of polyurethane shoe-sole；And isocyanates increases significantly
The hard segment content of reactant, ensure that the hardness and strength index of sole.
The purpose of the present invention two is to provide a kind of preparation method of hydrolysis resistant polyurethane sole, be prepared using this method
Sole hydrolytic resistance is good.
To achieve the above object two, the present invention provides following technical solutions：
A kind of preparation method of hydrolysis resistant polyurethane sole, which is characterized in that include the following steps：
Step 1 weighs component A and B component in proportion；
Step 2 heats component A 1-2 hours under the conditions of 100-110 DEG C, and metal-chelator and isothiazoline are added in after melting
Ketone is uniformly mixed, and is injected in the first batch can of bottler placer；
B component is uniformly mixed and is heated 2-3 hours under the conditions of 120-130 DEG C, injects the second batch can of bottler placer by step 3
In；
Step 4 pours into mixed component A, metal-chelator and isothiazolinone and B component in footwear mould, and footwear mould is put
Enter in foaming machine and foam；
Step 5, foam postcooling, repairs, and molding obtains the hydrolysis resistant polyurethane sole.
Through the above technical solutions, the present invention introduces polyether polyol in polyurethane shoe-sole, the ether in polyether polyol
Functional group has preferable anti-hydrolytic performance, the shortcomings that overcoming polyester-type；Simultaneously using non-metallic catalyst, avoid introducing energy
The metal ion for enough hydrolyzing polyurethane improves the anti-hydrolytic performance of polyurethane shoe-sole；When adding metal-chelator will produce
Inside the impurity metal ion inclusion to chelating agent of introducing, so as to further improve the anti-hydrolytic performance of polyurethane shoe-sole；Again plus
Enter preservative isothiazolinone and inhibit or kill microorganism, avoid microorganism that polyurethane shoe-sole is caused to be degraded；With the different of phenyl ring
Cyanate improves the crystallinity of polyurethane so that diffusion of moisture speed slows down, so as to improve the hydrolytic resistance of polyurethane shoe-sole
Can, five cooperate, synergistic so that and the anti-hydrolytic performance of the hydrolysis resistant polyurethane sole in the present invention greatly promotes,
Extend its service life in wet environment.
In conclusion compared with prior art, the invention has the advantages that：
(1) present invention introduces polyether polyol in polyurethane shoe-sole, and polyurethane shoe improves in the ether functional group in polyether polyol
The anti-hydrolytic performance at bottom；
(2) present invention is avoided introducing the metal ion that can hydrolyze polyurethane, is added metal chelating using non-metallic catalyst
Mixture includes the impurity metal ion introduced when producing to inside chelating agent, so as to further improve the water-fast of polyurethane shoe-sole
Solve performance；
(3) present invention using preservative isothiazolinone inhibits or kills microorganism, and microorganism is avoided to cause polyurethane shoe-sole
Degradation；
(4) present invention improves the crystallinity of polyurethane using the isocyanates with phenyl ring so that and diffusion of moisture speed slows down, from
And improve the anti-hydrolytic performance of polyurethane shoe-sole；
(5) polyether polyol, non-metallic catalyst, metal-chelator, isothiazolinone, the isocyanates phase interworking with phenyl ring
It closes, it is synergistic so that the anti-hydrolytic performance of the hydrolysis resistant polyurethane sole in the present invention greatly promotes, and extends it in moist ring
Service life in border.
Description of the drawings
Fig. 1 is the process flow chart of the present invention.
Specific embodiment
With reference to the accompanying drawings and examples, the present invention will be described in detail.
Embodiment 1：A kind of hydrolysis resistant polyurethane sole, each component and its corresponding parts by weight are as shown in table 1, technique
Acquisition is made by the steps with reference to Fig. 1 in flow：
Step 1 weighs component A and B component in proportion；
Step 2 heats component A 1 hour under the conditions of 100 DEG C, and metal-chelator and isothiazolinone are added in after melting, is stirred
It mixes uniformly mixed, injects in the first batch can of bottler placer；
B component is uniformly mixed and is heated 2 hours under the conditions of 120 DEG C, injected in the second batch can of bottler placer by step 3；
Step 4 pours into mixed component A, metal-chelator and isothiazolinone and B component in footwear mould, and footwear mould is put
Enter in foaming machine and foam；
Step 5, foam postcooling, repairs, and molding obtains the hydrolysis resistant polyurethane sole.
Embodiment 2-8：A kind of hydrolysis resistant polyurethane sole, the difference lies in, each components and its corresponding with embodiment 1
Parts by weight it is as shown in table 1.
Each component and its parts by weight in 1 embodiment 1-8 of table
Embodiment 9-16：A kind of hydrolysis resistant polyurethane sole, the difference lies in, each components and its corresponding with embodiment 1
Parts by weight are as shown in table 2.
Each component and its parts by weight in 2 embodiment 9-16 of table
Embodiment 17-25：A kind of hydrolysis resistant polyurethane sole, the difference lies in, each components and its corresponding with embodiment 1
Parts by weight are as shown in table 3.
Each component and its parts by weight in 3 embodiment 17-25 of table
Embodiment 26：A kind of hydrolysis resistant polyurethane sole, the difference lies in be made by the steps and obtain with embodiment 1
：
Step 1 weighs component A and B component in proportion；
Step 2 heats component A 1 hour under the conditions of 110 DEG C, and metal-chelator and isothiazolinone are added in after melting, is stirred
It mixes uniformly mixed, injects in the first batch can of bottler placer；
B component is uniformly mixed and is heated 2 hours under the conditions of 120 DEG C, injected in the second batch can of bottler placer by step 3；
Step 4 pours into mixed component A, metal-chelator and isothiazolinone and B component in footwear mould, and footwear mould is put
Enter in foaming machine and foam；
Step 5, foam postcooling, repairs, and molding obtains the hydrolysis resistant polyurethane sole.
Embodiment 27：A kind of hydrolysis resistant polyurethane sole, the difference lies in make as follows with embodiment 1
It is standby to obtain：
Step 1 weighs component A and B component in proportion；
Step 2 heats component A 2 hours under the conditions of 100 DEG C, and metal-chelator and isothiazolinone are added in after melting, is stirred
It mixes uniformly mixed, injects in the first batch can of bottler placer；
B component is uniformly mixed and is heated 2 hours under the conditions of 120 DEG C, injected in the second batch can of bottler placer by step 3；
Step 4 pours into mixed component A, metal-chelator and isothiazolinone and B component in footwear mould, and footwear mould is put
Enter in foaming machine and foam；
Step 5, foam postcooling, repairs, and molding obtains the hydrolysis resistant polyurethane sole.
Embodiment 28：A kind of hydrolysis resistant polyurethane sole, the difference lies in make as follows with embodiment 1
It is standby to obtain：
Step 1 weighs component A and B component in proportion；
Step 2 heats component A 1 hour under the conditions of 100 DEG C, and metal-chelator and isothiazolinone are added in after melting, is stirred
It mixes uniformly mixed, injects in the first batch can of bottler placer；
B component is uniformly mixed and is heated 2 hours under the conditions of 130 DEG C, injected in the second batch can of bottler placer by step 3；
Step 4 pours into mixed component A, metal-chelator and isothiazolinone and B component in footwear mould, and footwear mould is put
Enter in foaming machine and foam；
Step 5, foam postcooling, repairs, and molding obtains the hydrolysis resistant polyurethane sole.
Embodiment 29：A kind of hydrolysis resistant polyurethane sole, the difference lies in make as follows with embodiment 1
It is standby to obtain：
Step 1 weighs component A and B component in proportion；
Step 2 heats component A 1 hour under the conditions of 100 DEG C, and metal-chelator and isothiazolinone are added in after melting, is stirred
It mixes uniformly mixed, injects in the first batch can of bottler placer；
B component is uniformly mixed and is heated 3 hours under the conditions of 120 DEG C, injected in the second batch can of bottler placer by step 3；
Step 4 pours into mixed component A, metal-chelator and isothiazolinone and B component in footwear mould, and footwear mould is put
Enter in foaming machine and foam；
Step 5, foam postcooling, repairs, and molding obtains the hydrolysis resistant polyurethane sole.
Comparative example 1：A kind of hydrolysis resistant polyurethane sole, the difference lies in be added without polypropylene oxide with embodiment 1
Glycol.
Comparative example 2：A kind of hydrolysis resistant polyurethane sole, the difference lies in the weight such as replace with by morpholine with embodiment 1
Measure the potassium acetate of number.
Comparative example 3：A kind of hydrolysis resistant polyurethane sole, the difference lies in different by diphenyl methane two with embodiment 1
Cyanate such as replaces at the hexamethylene diisocyanate of parts by weight.
Comparative example 4：A kind of thermoplastic poly ammonia disclosed in Chinese invention patent using Publication No. CN103073697A
The processing technology of ester elastomer prepares hydrolysis resistant polyurethane sole.
Test anti-hydrolytic performance test
Test specimen：Using the hydrolysis resistant polyurethane sole obtained in embodiment 1-29 as test specimen 1-29, using comparison
The hydrolysis resistant polyurethane sole obtained in example 1-4 is as control sample 1-4.
Test method：Every group of sample takes ten respectively, with reference to GB/T20991-2007《The test side of Individual protection equitment footwear
Method》In 8.5 regulation testing experiment sample 1-29 and control sample 1-4 anti-hydrolytic performance, give up every group maximum value and
Minimum value, remaining to take its average value, finished product Typical physical mechanical property standard is with reference to QB/T4345-2012《It uses at protective footwear bottom
Polyurethane resin》In regulation, notch growth≤6mm.
Result of the test：The anti-hydrolytic performance testing result of test specimen 1-29 and control sample 1-4 is as shown in table 4.By table 4
It is found that the notch increment of test specimen 1-29 is significantly less than control sample 1-4, by test specimen 1 and test specimen 6-14
After test result is it is found that add in metal-chelator and/or preservative isothiazolinone, notch increment further reduces, and says
Bright metal-chelator and isothiazolinone can enhance the anti-hydrolytic performance of hydrolysis resistant polyurethane sole, and polyethers in the present invention
Polyalcohol, non-metallic catalyst, metal-chelator, isothiazolinone, the isocyanates with phenyl ring cooperate, synergistic,
So that the anti-hydrolytic performance of the hydrolysis resistant polyurethane sole in the present invention greatly promotes, extend it and use the longevity in wet environment
Life.
The anti-hydrolytic performance testing result of table 4 test specimen 1-29 and control sample 1-4
Test two physical and mechanical property tests
Test method：With reference to QB/T4345-2012《Protective footwear bottom polyurethane resin》In regulation testing experiment sample 1,6,
11st, 14 Typical physical mechanical property, and be recorded in table.
Result of the test：1,6,11,14 physical and mechanical property testing result of test specimen is as shown in table 5.
5 test specimen of table, 1,6,11,14 physical and mechanical property testing result
The above is only the preferred embodiment of the present invention, and protection scope of the present invention is not limited merely to above-described embodiment,
All technical solutions belonged under thinking of the present invention all belong to the scope of protection of the present invention.It should be pointed out that for the art
For those of ordinary skill, several improvements and modifications without departing from the principles of the present invention, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of hydrolysis resistant polyurethane sole, which is characterized in that including component A and B component, component A includes following parts by weight
Component：
40-60 parts of polyether polyol；
30-50 parts of polyester polyol；
1-2 parts of non-metallic catalyst；
1-5 parts of chain extender；
1-2 parts of foam stabilizer；
1-2 parts of water；
B component includes the component of following parts by weight：
20-40 parts of isocyanates；
10-30 parts of polyethylene glycol adipate.
2. hydrolysis resistant polyurethane sole according to claim 1, which is characterized in that the hydrolysis resistant polyurethane sole also wraps
Include 0.1-0.5 parts of metal-chelators.
3. hydrolysis resistant polyurethane sole according to claim 2, which is characterized in that the metal-chelator includes amino three
Any one in methylene phosphonic acid, ethylene diamine tetra methylene phosphonic acid, aminotrimethylenephosphonic acid.
4. hydrolysis resistant polyurethane sole according to claim 1, which is characterized in that the hydrolysis resistant polyurethane sole also wraps
Include 0.5-2.5 parts of isothiazolinone.
5. hydrolysis resistant polyurethane sole according to claim 1, which is characterized in that the polyether polyol includes polyoxygenated
Propylene glycol, polyethylene glycol oxide are copolymerized any one in ethoxylated polyhydric alcohol, polytetrahydrofuran polyol.
6. hydrolysis resistant polyurethane sole according to claim 1, which is characterized in that the polyester polyol includes poly- certain herbaceous plants with big flowers two
Acid-polybutadiene binary alcohol esters polyalcohol, polyethylene glycol diethylene glycol sebacic acid ester polyol, polyadipate ethylene glycol diethyl two
Any one in alcohol glycerine ester polyol.
7. hydrolysis resistant polyurethane sole according to claim 1, which is characterized in that the non-metallic catalyst includes
Quinoline, N, any one in N dimethyl cyclohexylamine, triethanolamine.
8. hydrolysis resistant polyurethane sole according to claim 1, which is characterized in that the chain extender includes ethylene glycol, first
Any one in base propylene glycol, glycerine；The foam stabilizer is dimethyl siloxane or polyether silicone.
9. hydrolysis resistant polyurethane sole according to claim 1, which is characterized in that the isocyanates includes diphenylmethyl
Any one in alkane diisocyanate, two cyclohexyl methane diisocyanates, naphthalene diisocyanate.
10. a kind of preparation method of hydrolysis resistant polyurethane sole, which is characterized in that include the following steps：
Step 1 weighs component A and B component in proportion；
Step 2 heats component A 1-2 hours under the conditions of 100-110 DEG C, and metal-chelator and isothiazoline are added in after melting
Ketone is uniformly mixed, and is injected in the first batch can of bottler placer；
B component is uniformly mixed and is heated 2-3 hours under the conditions of 120-130 DEG C, injects the second batch can of bottler placer by step 3
In；
Step 4 pours into mixed component A, metal-chelator and isothiazolinone and B component in footwear mould, and footwear mould is put
Enter in foaming machine and foam；
Step 5, foam postcooling, repairs, and molding obtains the hydrolysis resistant polyurethane sole.
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| WO2020107136A1 (en) * | 2018-11-26 | 2020-06-04 | 福建省晋江泉发骑士鞋业有限公司 | Etpu sole material and preparation method and application thereof |
| CN111499826A (en) * | 2020-04-08 | 2020-08-07 | 上海抚佳精细化工有限公司 | Thermoplastic polyurethane elastomer and preparation method thereof |
| CN112980383A (en) * | 2019-12-13 | 2021-06-18 | 万华化学集团股份有限公司 | Adhesive for PP (polypropylene) base material as well as preparation method and application thereof |
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| WO2020107136A1 (en) * | 2018-11-26 | 2020-06-04 | 福建省晋江泉发骑士鞋业有限公司 | Etpu sole material and preparation method and application thereof |
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