CN117164809A - Bio-based polyurethane composite material applied to insoles and preparation method thereof - Google Patents
Bio-based polyurethane composite material applied to insoles and preparation method thereof Download PDFInfo
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- CN117164809A CN117164809A CN202311285908.7A CN202311285908A CN117164809A CN 117164809 A CN117164809 A CN 117164809A CN 202311285908 A CN202311285908 A CN 202311285908A CN 117164809 A CN117164809 A CN 117164809A
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 64
- 239000004814 polyurethane Substances 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 229920005862 polyol Polymers 0.000 claims abstract description 57
- 150000003077 polyols Chemical class 0.000 claims abstract description 56
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 239000003381 stabilizer Substances 0.000 claims abstract description 16
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 15
- 239000004970 Chain extender Substances 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 11
- 239000004632 polycaprolactone Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 9
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- GAWWVVGZMLGEIW-GNNYBVKZSA-L zinc ricinoleate Chemical compound [Zn+2].CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O.CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O GAWWVVGZMLGEIW-GNNYBVKZSA-L 0.000 claims description 16
- 229940100530 zinc ricinoleate Drugs 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 239000004359 castor oil Substances 0.000 claims description 14
- 235000019438 castor oil Nutrition 0.000 claims description 14
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 14
- 239000003921 oil Substances 0.000 claims description 13
- 235000019198 oils Nutrition 0.000 claims description 13
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- 229920000570 polyether Polymers 0.000 claims description 11
- 235000012424 soybean oil Nutrition 0.000 claims description 11
- 239000003549 soybean oil Substances 0.000 claims description 11
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 9
- 150000001343 alkyl silanes Chemical class 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 125000005456 glyceride group Chemical group 0.000 claims description 8
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 239000012970 tertiary amine catalyst Substances 0.000 claims description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 2
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- 229960002887 deanol Drugs 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- 239000012972 dimethylethanolamine Substances 0.000 claims description 2
- 229940049964 oleate Drugs 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 230000001877 deodorizing effect Effects 0.000 abstract 1
- 230000006835 compression Effects 0.000 description 18
- 238000007906 compression Methods 0.000 description 18
- 239000000463 material Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 5
- SCPWMSBAGXEGPW-UHFFFAOYSA-N dodecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OC)(OC)OC SCPWMSBAGXEGPW-UHFFFAOYSA-N 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 235000010469 Glycine max Nutrition 0.000 description 3
- 244000068988 Glycine max Species 0.000 description 3
- 239000003242 anti bacterial agent Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229920005906 polyester polyol Polymers 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 206010040904 Skin odour abnormal Diseases 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960000686 benzalkonium chloride Drugs 0.000 description 1
- XIWFQDBQMCDYJT-UHFFFAOYSA-M benzyl-dimethyl-tridecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 XIWFQDBQMCDYJT-UHFFFAOYSA-M 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229940071160 cocoate Drugs 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The application relates to the field of shoe pads, and in particular discloses a bio-based polyurethane composite material applied to shoe pads and a preparation method thereof, wherein the bio-based polyurethane composite material comprises a component A and a component B, and the component A is prepared from the following raw materials in parts by weight: 42 to 62 parts of bio-based polyol, 3 to 6 parts of chain extender, 1 to 2 parts of stabilizer, 0.5 to 1.5 parts of catalyst and 0.2 to 0.4 part of water; the component B is prepared from the following raw materials in parts by weight: 20-40 parts of diisocyanate, 5-15 parts of polycaprolactone polyol, 5-10 parts of antibacterial auxiliary agent and 0.1-0.3 part of antioxidant; the preparation method comprises the following steps: mixing the raw materials, heating and vacuumizing to obtain a component A; mixing the raw materials, heating and vacuumizing to obtain the component B. The preparation method is simple, and the prepared bio-based polyurethane composite material has good biodegradability and system stability, and is good in elasticity, difficult to deform, good in antibacterial deodorizing performance and environmental friendliness when applied to insoles.
Description
Technical Field
The application relates to the field of bio-based polyurethane materials, in particular to a bio-based polyurethane composite material applied to insoles and a preparation method thereof.
Background
Polyurethane materials have excellent physical properties and good processability and are widely applied to insoles.
Polyurethane materials are prepared by reacting polyols containing alcoholic hydroxyl groups with isocyanate, and commonly used polyols include polyether polyols and polyester polyols, and all of the raw materials are derived from non-renewable petroleum raw materials, so that the polyurethane prepared from the polyols has low degradability and environmental friendliness, and therefore, the research on using bio-based polyols to replace common polyols is carried out to prepare the polyurethane materials.
Common bio-based polyols are generally derived from vegetable oil, vegetable fibers, polylactic acid fibers and the like, polyurethane materials prepared from the bio-based polyols have better biodegradability, but mechanical properties are lower than those of common polyols, after the polyurethane materials prepared from the bio-based polyols are applied to insoles, the prepared insoles are easy to deform after being used for a period of time, the elasticity is lower, and in addition, the insoles are easy to grow a lot of bacteria in the use process, smelly feet appear, so that the application of the bio-based polyurethane materials in the insoles is reduced.
Disclosure of Invention
The application provides a bio-based polyurethane composite material applied to insoles and a preparation method thereof, aiming at solving the problems that the conventionally used bio-based polyurethane material is easy to deform, has low elasticity and is easy to grow bacteria when applied to insoles.
In a first aspect, the application provides a bio-based polyurethane composite material applied to insoles, which adopts the following technical scheme:
the biological polyurethane composite material applied to the insoles consists of a component A and a component B, wherein the component A is prepared from the following raw materials in parts by weight: 42 to 62 parts of bio-based polyol, 3 to 6 parts of chain extender, 1 to 2 parts of stabilizer, 0.5 to 1.5 parts of catalyst and 0.2 to 0.4 part of water; the component B is prepared from the following raw materials in parts by weight: 20-40 parts of diisocyanate, 5-15 parts of polycaprolactone polyol, 5-10 parts of antibacterial auxiliary agent and 0.1-0.3 part of antioxidant.
By adopting the technical scheme, the bio-based polyurethane composite material provided by the application is composed of the component A and the component B, wherein the component A and the component B are respectively stored, the system performance is stable, when the bio-based polyurethane composite material is applied to insoles, the component A and the component B are mixed and reacted according to the proportion of the dosage ratio of 1 (0.82-0.92), and the prepared insoles have better elasticity, smaller permanent compression deformation rate, antibacterial property and biodegradability.
When the polyurethane composite material is mixed, under the action of a catalyst, the bio-based polyol and the polycaprolactone polyol provide alcoholic hydroxyl groups, the chain extender can react with diisocyanate, the chain extender has a good chain extension crosslinking effect, the elasticity and compression deformation resistance of the prepared insole can be further improved, water is used as a foaming agent, the stabilizer has the effects of stabilizing system reaction and homogenizing, the system reacts stably and foams under the action of the stabilizer, the prepared insole has a good elasticity and compression deformation resistance, the antioxidant has a good antioxidant effect, the weather resistance of the prepared insole can be improved, the antibacterial auxiliary agent has a good antibacterial property, and the prepared bio-based polyurethane composite material can be further improved when being added into the component B, so that the antibacterial effect is good.
Preferably, the bio-based polyol is prepared from the following raw materials in parts by weight: 20 to 35 parts of epoxidized soybean oil, 40 to 60 parts of diglycol and 0.05 to 0.15 part of catalyst.
By adopting the technical scheme, the epoxidized soybean oil and the diglycol are subjected to hydroxylation reaction under the action of the catalyst, so that the prepared bio-based polyol containing soybean oil base contains ester groups on the main chain and long straight-chain ether groups on the side chain, and compared with conventionally used polyether polyol and polyester polyol, the molecular structure has better softness and multi-branch network structure, and the excellent performances of the polyether polyol and the polyester polyol are combined, so that the prepared bio-based polyurethane composite material has better softness, elasticity, biodegradability and the like, and has better elasticity, compression set resistance and environmental protection when being applied to insoles.
Preferably, the bio-based polyol is prepared by the steps of:
a1, adding 20-35 parts of epoxidized soybean oil, 40-60 parts of diethylene glycol and 0.05-0.15 part of catalyst into reaction equipment according to parts by weight, heating to 90-110 ℃ and reacting for 3-5 hours;
a2, cooling to 25-35 ℃, standing to separate an oil phase, adding 10-20 parts of 5-15 wt% sodium carbonate aqueous solution into the oil phase for washing, washing until the pH value is 8-9, continuously separating the oil phase, and carrying out reduced pressure distillation on the oil phase to obtain the bio-based polyol; the catalyst is concentrated sulfuric acid.
Through adopting the technical scheme, firstly, under the better condition, concentrated sulfuric acid is used as a catalyst to enable the epoxidized soybean oil and the diglycol to react, so that the soybean-based bio-based polyol is prepared, the prepared sodium carbonate aqueous solution with the better concentration in the bio-based polyol is washed to remove acid impurities in the soybean-based polyol, then reduced pressure distillation is carried out to remove low-boiling impurities in the soybean-based polyol, and further the bio-based polyol is prepared.
Preferably, the antibacterial auxiliary agent is formed by mixing zinc ricinoleate, castor oil and a long-chain alkyl silane coupling agent with the dosage ratio of (0.4-0.6) to (2-3).
By adopting the technical scheme, the zinc ricinoleate is an antibacterial material containing active zinc, the castor oil is vegetable oil containing polyhydroxy, the castor oil is used as a dispersing carrier of the zinc ricinoleate, the zinc ricinoleate is stably dispersed into a long-chain alkyl silane coupling agent, the zinc ricinoleate, the castor oil and the long-chain alkyl silane coupling agent are compounded in a better proportion, the prepared antibacterial auxiliary agent can be stably dispersed into the component B under the synergistic effect of the zinc ricinoleate, the castor oil and the long-chain alkyl silane coupling agent, the antibacterial auxiliary agent can be subjected to further crosslinking reaction with diisocyanate, and when the prepared biological polyurethane composite material is applied to insoles, the elasticity and compression set resistance of the insoles can be further improved while the antibacterial property and the biodegradability of the insoles are improved.
Preferably, the chain extender is one or a combination of ethylene glycol, butanediol, trimethylolpropane, ethylenediamine, hexamethylenediamine and isophorone diamine.
By adopting the technical scheme, the chain extender can further carry out crosslinking reaction with diisocyanate, so that the prepared polyurethane composite material reacts to form a macromolecular reticular crosslinking structure, and the elasticity and compression deformation resistance of the prepared insole are further improved.
Preferably, the stabilizer consists of polyether modified organic silicon and coco glyceride with the dosage ratio of 1 (0.1-0.3).
By adopting the technical scheme, the polyether modified organic silicon and the cocoanut glyceride with the optimal proportion can improve the foaming uniformity and the reaction stability of the polyurethane composite material, form a uniform and stable foaming system, and improve the uniform elasticity and the permanent compression set resistance of the insole formed by foaming.
Preferably, the diisocyanate is one or a combination of toluene diisocyanate, polymethylene polyphenyl isocyanate, diphenylmethane diisocyanate and liquefied MDI.
By adopting the technical scheme, the diisocyanate provides isocyanate groups to react with polyol hydroxyl groups, and the prepared bio-based polyurethane composite material has good reaction stability, can stably react and uniformly foam when being applied to insoles, so that the insoles formed by the method have good elasticity and permanent compression set resistance.
Preferably, the catalyst consists of an organotin catalyst and a tertiary amine catalyst in the dosage ratio of 1 (0.5-0.8), wherein the organotin catalyst is any one of stannous octoate, stannous oleate and dibutyltin dilaurate, and the tertiary amine catalyst is any one of triethylenediamine, dimethylethanolamine, N-methyl morpholine and N, N-dimethylcyclohexane.
By adopting the technical scheme, the tertiary amine catalyst and the organotin catalyst with a better proportion are used as the catalyst for the reaction, so that the stability and the sufficiency of the reaction can be improved, and the bio-based polyurethane composite material with stable performance applied to the insoles can be further prepared.
In a second aspect, the application provides a preparation method of a bio-based polyurethane composite material applied to insoles, which adopts the following technical scheme:
the preparation method of the bio-based polyurethane composite material applied to the insoles comprises the following preparation steps:
adding the biological polyol and the chain extender into reaction equipment, heating, vacuumizing, uniformly stirring, cooling, adding the stabilizer, the catalyst and water, uniformly stirring, discharging, and sealing for preservation to obtain a component A;
adding diisocyanate, polycaprolactone polyol and an antibacterial auxiliary agent into reaction equipment, heating, vacuumizing, stirring, adding an antioxidant after the reaction, uniformly stirring, cooling, discharging, and sealing for preservation to obtain the component B.
By adopting the technical scheme, the biological polyol and the chain extender are uniformly mixed and dispersed under the conditions of heating and vacuumizing, the temperature is lowered after the biological polyol and the chain extender are uniformly dispersed, the purpose of lowering the temperature is to ensure the stability of a system, and the stabilizer, the catalyst and the water are added for uniform dispersion, so that the component A of the biological polyurethane composite material is prepared; uniformly mixing and dispersing polycaprolactone, diisocyanate and an antibacterial auxiliary agent under the conditions of heating and vacuumizing, and then adding an antioxidant to prepare a component B of the bio-based polyurethane composite material, wherein the prepared component A and component B are independent stable systems, are easy to store, and are mixed and reacted according to a proportion during use.
Preferably, in the step of preparing the component A, the temperature is raised to 60-75 ℃, the vacuum degree of vacuumizing is minus 0.05 to minus 0.08MPa, the first stirring time is 1-2 h, the temperature is lowered to 20-35 ℃, and the second stirring time is 30-60 min; in the preparation step of the component B, the temperature is raised to 70-85 ℃, the vacuumizing vacuum degree is minus 0.05-minus 0.08MPa, the first stirring time is 1-3 h, the second stirring time is 10-30 min, and the cooling temperature is 20-35 ℃.
By adopting the technical scheme, the component A and the component B of the bio-based polyurethane composite material with stable performance and system can be prepared under the better mixing condition.
In summary, the application has the following beneficial effects:
1. the application relates to a bio-based polyurethane composite material applied to insoles, which takes bio-based polyol, chain extender, stabilizer, catalyst and water as a component A, diisocyanate, polycaprolactone polyol, antibacterial auxiliary agent and antioxidant as a component B, and when the bio-based polyurethane composite material is applied to insoles, the component A and the component B are mixed and reacted in a better proportion, so that the prepared insoles have better elasticity, compression deformation resistance, antibacterial property and biodegradability.
2. The bio-based polyol containing soybean oil is prepared by using epoxidized soybean oil, diglycol and concentrated sulfuric acid catalyst to react and through alkali washing separation, water washing separation and reduced pressure distillation, the main chain of the bio-based polyol contains ester groups and the side chains of the bio-based polyol contain long linear chain ether groups, the molecular structure has good flexibility and a multi-branch reticular structure, and the prepared bio-based polyurethane composite material has good elasticity, compression deformation resistance and environmental protection when being applied to insoles.
3. By using zinc ricinoleate, castor oil and long-chain alkyl silane coupling agent with a better proportion as antibacterial auxiliary agents and castor oil as a dispersing carrier of the zinc ricinoleate, the zinc ricinoleate can be stably dispersed into the long-chain alkyl silane coupling agent, and under the synergistic effect of the zinc ricinoleate, the prepared antibacterial auxiliary agent and diisocyanate can be subjected to further crosslinking reaction, and the prepared bio-based polyurethane composite material can be applied to insoles, so that the antibacterial property and the biodegradability of the insoles are improved, and meanwhile, the elasticity and the compression set resistance of the insoles are further improved.
4. The preparation method of the application is simple and easy to operate, and the prepared double-component bio-based composite material is stored separately and has stable performance and system.
Detailed Description
The present application will be described in further detail with reference to examples.
The following are sources and specifications of some of the raw materials of the present application, and the raw materials used in the preparation examples and examples of the present application can be obtained commercially:
1. epoxidized soybean oil: molecular weight 1000, epoxy value greater than 6%;
2. diethylene glycol: glycol ether, density 1.106g/cm 3 ；
3. Zinc ricinoleate: purity 98%, technical grade, white powder;
4. castor oil: molecular weight 930-935, content 99.9%, hydroxyl content 5%, hydroxyl average functionality 2.7;
5. polyether modified silicone: ceramic DC5043;
6. glycerol cocoate: PEG-7, 98%;
7. polycaprolactone polyol: polycaprolactone diol, molecular weight 2000, hydroxyl value 56mgKOH/g, melting point 45-55deg.C.
Preparation of biobased polyol
Preparation example 1
Preparation example 1 discloses a bio-based polyol prepared by the steps of:
a1, adding 2kg of epoxidized soybean oil, 4kg of diglycol and 5g of concentrated sulfuric acid serving as catalysts into a reaction kettle, heating to 90 ℃, and reacting for 3 hours;
a2, cooling to 25 ℃, standing to separate an oil phase, adding 1kg of 5wt% sodium carbonate aqueous solution into the oil phase for washing, then washing for 2-3 times, washing until the pH value is 8, continuously separating the oil phase, carrying out reduced pressure distillation on the oil phase, and removing low-boiling impurities in the oil phase to obtain the bio-based polyol.
PREPARATION EXAMPLES 2-3
Preparation examples 2-3 disclose a bio-based polyol differing from preparation example 1 in the preparation conditions and the amounts of raw materials, see in particular Table 1 below.
TABLE 1 raw materials amounts and preparation conditions of preparation examples 1 to 3
Preparation of comparative example 1
Preparation comparative example 1 discloses a bio-based polyol, which is different from preparation example 1 in that diethylene glycol is replaced with ethylene glycol in equal amount, and the other is the same as preparation example 1.
Examples
Example 1
Example 1 discloses a bio-based polyurethane composite material applied to insoles, which is prepared by the following preparation steps:
adding 4.2kg of commercial bio-based polyol and 0.3kg of ethylene glycol as chain extender into a reaction kettle, heating to 60 ℃, vacuumizing, stirring for 1h, cooling to 20 ℃ and then adding a stabilizer consisting of 0.05kg of polyether modified organosilicon and 0.05kg of coco glyceride, 33.33g of stannous octoate as an organotin catalyst, 16.67g of triethylenediamine as a tertiary amine catalyst and 20g of water, stirring for 30min, discharging after uniform stirring, and sealing and preserving to obtain a component A, wherein the hydroxyl value of the commercial bio-based polyol is 45-60mg KOH/g, and the viscosity is 800-1500 Pa.s;
adding 2kg of toluene diisocyanate as diisocyanate, 0.5kg of polycaprolactone polyol and an antibacterial auxiliary agent prepared by mixing 0.1kg of zinc ricinoleate, 0.1kg of castor oil and 0.3kg of dodecyl trimethoxy silane as a long-chain alkyl silane coupling agent into a reaction kettle, heating to 70 ℃, vacuumizing to the vacuum degree of minus 0.05MPa, stirring for 1h, adding 10g of antioxidant 1010 after stirring reaction, stirring for 10min, cooling to 20 ℃, discharging and sealing for preservation to obtain the component B.
Examples 2 to 3
Examples 2-3 disclose a bio-based polyurethane composite applied to an insole, which is different from example 1 in the amount of raw materials and preparation conditions, see in particular table 2 below.
TABLE 2 raw materials amounts and preparation conditions Table for examples 1-3
Examples 4 to 7
Examples 4-7 disclose a bio-based polyurethane composite for shoe insoles, differing from example 1 in the source of bio-based polyols, see in particular table 3 below.
TABLE 3 Source list of biobased polyols of examples 4-7
| Examples | Bio-based polyol sources |
| Example 4 | Preparation example 1 |
| Example 5 | Preparation example 2 |
| Example 6 | Preparation example 3 |
| Example 7 | Preparation of comparative example 1 |
Example 8
Example 8 discloses a bio-based polyurethane composite material applied to insoles, which is different from example 4 in the proportion of antibacterial auxiliary agent, wherein the dosage ratio of zinc ricinoleate, castor oil and dodecyl trimethoxysilane is 1:0.4:2, and the other materials are the same as example 4.
Example 9
Example 9 discloses a bio-based polyurethane composite material applied to insoles, which is different from example 4 in the proportion of antibacterial auxiliary agent, wherein the dosage ratio of zinc ricinoleate, castor oil and dodecyl trimethoxysilane is 1:0.6:3, and the other materials are the same as example 4.
Example 10
Example 10 discloses a bio-based polyurethane composite applied to insoles, which is different from example 8 in the proportion of stabilizer, the ratio of polyether modified silicone to coco glyceride is 1:0.1, and otherwise the same as example 8.
Example 11
Example 11 discloses a bio-based polyurethane composite applied to an insole, which is different from example 8 in the proportion of stabilizer, the ratio of polyether modified silicone to coco glyceride is 1:0.3, and the other is the same as example 8.
Example 12
Example 12 discloses a bio-based polyurethane composite applied to an insole, which is different from example 4 in that the antibacterial auxiliary agent is replaced with dodecyl trimethoxysilane in equal amount, and the other is the same as example 4.
Example 13
Example 13 discloses a bio-based polyurethane composite applied to an insole, which is different from example 4 in that the stabilizer is different from that of example 4 in that the equivalent amount of coco glyceride is replaced by polyether modified silicone, and the other is the same as that of example 4.
Comparative example
Comparative example 1
Comparative example 1 discloses a bio-based polyurethane composite applied to an insole, which is different from example 1 in that the antibacterial agent is a commercially available quaternary ammonium salt antibacterial agent (benzalkonium chloride), and otherwise is the same as example 1.
Application example
Application example 1
Application example 1 discloses an insole, wherein the component A and the component B of the bio-based polyurethane composite material prepared in example 1 are mixed and stirred for 30min according to the mass ratio of 1:0.82, then are added into a mold, reaction curing is carried out at the temperature of 70 ℃, curing is carried out for 30min, and then the mold is opened and cutting is carried out, so that the insole with the thickness of 0.45+/-0.02 cm is prepared.
Application examples 2 to 3
Application examples 2-3 disclose an insole differing from example 1 in the processing conditions and the source of the bio-based polyurethane composite, see in particular table 4 below.
TABLE 4 preparation conditions Table of application examples 1-3
Application examples 4 to 15
Application examples 4-15 disclose an insole differing from application example 1 in the source of the bio-based polyurethane composite, see in particular table 5 below.
TABLE 5 Source list of biobased polyurethane composites of application examples 4-15
| Application example | Bio-based polyurethane composite sources |
| Application example 4 | Example 4 |
| Application example 5 | Example 5 |
| Application example 6 | Example 6 |
| Application example 7 | Example 7 |
| Application example 8 | Example 8 |
| Application example 9 | Example 9 |
| Application example 10 | Example 10 |
| Application example 11 | Example 11 |
| Application example 12 | Example 12 |
| Application example 13 | Example 13 |
| Application example 14 | Comparative example 1 |
Performance test the following performance tests were performed on the insoles prepared in application examples 1 to 14:
(1) Elasticity test:
referring to the test method in GB/T1681, a rebound tester is used for testing the elasticity (unit:%) of the insole, and the detection result is detected and recorded;
(2) Permanent compression set test:
referring to the test method of ASTM D395-B-2003, a compression tester is used to perform a compression set (unit:%) test on the insole, and the test result is detected and recorded;
(3) Antibacterial performance test:
referring to the test methods in QB/T5191-2017 and QB/T2881-2013, after the insole is washed 10 times by using the commercial laundry detergent, the antibacterial rate (unit:%) of staphylococcus aureus and white ball is tested, and the detection result is detected and recorded;
(4) Bio-based content testing:
the insole prepared by reference to ASTM D6866-21 method B (AMS) standard test method for measuring biobased content in solid, liquid and gas samples by radioactive carbon analysis method is subjected to biobased content (unit:%) test, and the detection result is detected and recorded;
the following are the elastic, permanent compression set, antibacterial and biobased content test data of the insoles manufactured in application examples 1 to 14, with reference to table 6 below.
Table 6 performance test data sheet for insoles of application examples 1 to 14
As can be seen from the combination of application examples 1 to 3 and application examples 4 to 7 and the combination of Table 6, the bio-based polyurethane composite material prepared by using the bio-based polyol prepared by the preparation method of the present application is applied to insoles, the elasticity of the prepared insoles is improved by up to 5%, the permanent compression set is reduced by 2.5%, the bio-based content is improved by 2.4%, and the performance of the prepared insoles is obviously reduced by replacing diethylene glycol with ethylene glycol in the same amount in application example 7.
As can be seen from the combination of application examples 4 to 6, application examples 8 to 9, application example 12 and comparative example 1 and the combination of Table 6, the insole prepared from the bio-based polyurethane composite material prepared by using the zinc ricinoleate, castor oil and long-chain alkyl silane coupling agent of the application has better elasticity, smaller permanent compression set, good antibacterial property and better biodegradability, the antibacterial auxiliary agent with better proportion is used in application examples 8 to 9, the performance is improved, the castor oil is not added in application example 12, the performance of the prepared insole is reduced compared with application example 4, the elasticity is increased, the permanent compression set rate is also obviously reduced, the antibacterial property is also reduced, the biodegradability is also reduced, and the conventional quaternary ammonium salt antibacterial agent is used in comparative example 1, and all the performances are obviously reduced.
In combination with application examples 4, application examples 8 to 9, application examples 10 to 11 and application example 13 and with Table 6, it can be seen that the performance of the insole made with the stabilizer in the preferred ratio is better, whereas the performance of the insole made with effort 13 without addition of coco glyceride is reduced.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (10)
1. The bio-based polyurethane composite material for the shoe pads is characterized by comprising a component A and a component B, wherein the component A is prepared from the following raw materials in parts by weight: 42 to 62 parts of bio-based polyol, 3 to 6 parts of chain extender, 1 to 2 parts of stabilizer, 0.5 to 1.5 parts of catalyst and 0.2 to 0.4 part of water; the component B is prepared from the following raw materials in parts by weight: 20-40 parts of diisocyanate, 5-15 parts of polycaprolactone polyol, 5-10 parts of antibacterial auxiliary agent and 0.1-0.3 part of antioxidant.
2. The bio-based polyurethane composite for shoe insoles according to claim 1, wherein the bio-based polyol is prepared from the following raw materials in parts by weight: 20 to 35 parts of epoxidized soybean oil, 40 to 60 parts of diglycol and 0.05 to 0.15 part of catalyst.
3. A biobased polyurethane composite for shoe insoles according to claim 2, wherein the biobased polyol is prepared by the steps of:
a1, adding 20-35 parts of epoxidized soybean oil, 40-60 parts of diethylene glycol and 0.05-0.15 part of catalyst into reaction equipment according to parts by weight, heating to 90-110 ℃ and reacting for 3-5 hours;
a2, cooling to 25-35 ℃, standing to separate an oil phase, adding 10-20 parts of 5-15 wt% sodium carbonate aqueous solution into the oil phase for washing, washing until the pH value is 8-9, continuously separating the oil phase, and carrying out reduced pressure distillation on the oil phase to obtain the bio-based polyol; the catalyst is concentrated sulfuric acid.
4. The bio-based polyurethane composite material applied to insoles according to claim 1, wherein the antibacterial auxiliary agent is formed by mixing zinc ricinoleate, castor oil and a long-chain alkyl silane coupling agent in a dosage ratio of 1 (0.4-0.6): 2-3.
5. The bio-based polyurethane composite for shoe insoles according to claim 1, wherein the chain extender is one or a combination of ethylene glycol, butylene glycol, trimethylol propane, ethylene diamine, hexamethylene diamine and isophorone diamine.
6. The bio-based polyurethane composite material for shoe pads according to claim 1, wherein the stabilizer consists of polyether modified organosilicon and coco glyceride with a dosage ratio of 1 (0.1-0.3).
7. The bio-based polyurethane composite for shoe insoles according to claim 1, wherein the diisocyanate is one or a combination of toluene diisocyanate, polymethylene polyphenyl isocyanate, diphenylmethane diisocyanate and liquefied MDI.
8. The bio-based polyurethane composite material applied to insoles according to claim 1, wherein the catalyst comprises an organotin catalyst and a tertiary amine catalyst in a dosage ratio of 1 (0.5-0.8), wherein the organotin catalyst is any one of stannous octoate, stannous oleate and dibutyltin dilaurate, and the tertiary amine catalyst is any one of triethylenediamine, dimethylethanolamine, N-methyl morpholine and N, N-dimethyl cyclohexane.
9. A method for preparing a bio-based polyurethane composite for insole according to any one of claims 1 to 8, comprising the following steps:
adding the biological polyol and the chain extender into reaction equipment, heating, vacuumizing, uniformly stirring, cooling, adding the stabilizer, the catalyst and water, uniformly stirring, discharging, and sealing for preservation to obtain a component A;
adding diisocyanate, polycaprolactone polyol and an antibacterial auxiliary agent into reaction equipment, heating, vacuumizing, stirring, adding an antioxidant after the reaction, uniformly stirring, cooling, discharging, and sealing for preservation to obtain the component B.
10. The bio-based polyurethane composite material for shoe pads according to claim 9, wherein in the step of preparing the component A, the temperature is raised to 60-75 ℃, the vacuum degree of vacuumizing is minus 0.05 to minus 0.08MPa, the first stirring time is 1-2 h, the temperature is lowered to 20-35 ℃, and the second stirring time is 30-60 min; in the preparation step of the component B, the temperature is raised to 70-85 ℃, the vacuumizing vacuum degree is minus 0.05-minus 0.08MPa, the first stirring time is 1-3 h, the second stirring time is 10-30 min, and the cooling temperature is 20-35 ℃.
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