CN117659334A - Polyether ester type polyurethane high-strength tear-resistant backrest and preparation method thereof - Google Patents
Polyether ester type polyurethane high-strength tear-resistant backrest and preparation method thereof Download PDFInfo
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- CN117659334A CN117659334A CN202311683489.2A CN202311683489A CN117659334A CN 117659334 A CN117659334 A CN 117659334A CN 202311683489 A CN202311683489 A CN 202311683489A CN 117659334 A CN117659334 A CN 117659334A
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- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 93
- 229920000570 polyether Polymers 0.000 title claims abstract description 93
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 68
- 239000004814 polyurethane Substances 0.000 title claims abstract description 68
- 150000002148 esters Chemical class 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 39
- 238000005187 foaming Methods 0.000 claims abstract description 37
- 238000002156 mixing Methods 0.000 claims abstract description 28
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 28
- 229920005862 polyol Polymers 0.000 claims abstract description 28
- 150000003077 polyols Chemical class 0.000 claims abstract description 28
- 239000004088 foaming agent Substances 0.000 claims abstract description 15
- 239000004970 Chain extender Substances 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 239000003381 stabilizer Substances 0.000 claims abstract description 13
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 27
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 24
- -1 polydimethylsiloxane Polymers 0.000 claims description 24
- 239000002202 Polyethylene glycol Substances 0.000 claims description 20
- 229920001223 polyethylene glycol Polymers 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 13
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 13
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 9
- XFDQLDNQZFOAFK-UHFFFAOYSA-N 2-benzoyloxyethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOC(=O)C1=CC=CC=C1 XFDQLDNQZFOAFK-UHFFFAOYSA-N 0.000 claims description 5
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004793 Polystyrene Substances 0.000 claims description 5
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 claims description 5
- 239000004005 microsphere Substances 0.000 claims description 5
- 229920002223 polystyrene Polymers 0.000 claims description 5
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 239000002861 polymer material Substances 0.000 abstract description 2
- 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 description 70
- 230000000052 comparative effect Effects 0.000 description 22
- 238000004519 manufacturing process Methods 0.000 description 17
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 12
- 239000000463 material Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 7
- 238000001514 detection method Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 230000002411 adverse Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920002725 thermoplastic elastomer Polymers 0.000 description 3
- 239000004636 vulcanized rubber Substances 0.000 description 3
- VNPRJHMMOKDEDZ-UHFFFAOYSA-L 6-methylheptyl 2-[dibutyl-[2-(6-methylheptoxy)-2-oxoethyl]sulfanylstannyl]sulfanylacetate Chemical compound CC(C)CCCCCOC(=O)CS[Sn](CCCC)(CCCC)SCC(=O)OCCCCCC(C)C VNPRJHMMOKDEDZ-UHFFFAOYSA-L 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000010009 beating Methods 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000004512 die casting Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000004224 protection Effects 0.000 description 2
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
Abstract
The application relates to the technical field of high polymer materials. The application discloses a polyether ester type polyurethane high-strength tear-resistant backrest and a preparation method thereof. The backrest comprises a component A and a component B, wherein the component A comprises polyether polyol A, polyester polyol B, a stabilizer, a chain extender, a foaming agent and a catalyst, and the component B comprises liquefied MDI and modified MDI. The preparation method comprises the following steps: s1, mixing polyether polyol A and polyester polyol B, adding a stabilizer, a chain extender, a foaming agent and a catalyst, and stirring to obtain a component A; s2, mixing the liquefied MDI with the modified MDI, and stirring to obtain a component B; s3, injecting the component A and the component B into a foaming machine, foaming, pouring and solidifying to obtain the backrest. The application also discloses application of the backrest in the field of electric bicycles and motorcycles. The polyether ester polyurethane prepared by the application has the advantages of high strength, high tearing resistance and strong tearing resistance.
Description
Technical Field
The application relates to the technical field of high polymer materials, in particular to a polyether ester type polyurethane high-strength tear-resistant backrest and a preparation method thereof.
Background
Electric bicycles and motor cycle backs refer to support and rest devices mounted behind the seat of the vehicle, which are located behind the seat, function to protect the rider or rider, and also provide lumbar and back support, providing riding comfort. The existing backrest generally comprises a supporting bottom shell, a fabric and a foaming body, and is fixed by manual cladding and gun nailing during production. Wherein the foaming body material is mostly formed by foaming polyether polyurethane.
The polyether polyurethane foam has good comfort and softness, but has relatively low strength, is easy to tear or deform, and reduces the stability and durability of the backrest, thereby reducing the service life of the backrest.
Moreover, the manual cladding and the gun nailing fixing are adopted during production, so that the production complexity and the labor cost are increased, the phenomena of glue spreading, cracking and the like are easy to occur, the production efficiency is low, and the service life is short.
Therefore, there is a need to develop a backrest with high strength, high tear resistance, no need of fixing gun nails, and high production efficiency.
Disclosure of Invention
In order to solve at least one technical problem, a polyether ester type polyurethane high-strength tearing-resistant backrest with high strength and high tearing resistance is developed.
On one hand, the polyether ester type polyurethane high-strength tear-resistant backrest provided by the application comprises an A component and a B component, wherein the weight ratio of the A component to the B component is 100: 60-70 parts;
the component A comprises 70-80 parts of polyether polyol A, 20-30 parts of polyester polyol B, 1-1.5 parts of stabilizer, 0.5-1 part of chain extender, 3-3.5 parts of foaming agent and 2-2.5 parts of catalyst;
the component B comprises liquefied MDI and modified MDI, and the weight ratio of the liquefied MDI to the modified MDI is 50-60: 40-50.
Through adopting above-mentioned technical scheme, this application adopts specific raw materials and ratio, and the comprehensive advantage of make full use of polyether type, polyester polyurethane material, the high-strength tear-resistant back of polyether ester type polyurethane that makes, intensity is high, and tear resistance is strong.
The weight ratio of the component A to the component B in the backrest can control the stability and strength of the backrest and provide higher tear resistance.
The polyether polyol A is added into the component A, so that the softness, the elasticity and the toughness of the polyether ester type polyurethane backrest can be provided, and the tear resistance can be improved; the polyester polyol B is added, so that the mechanical property of the polyether ester type polyurethane backrest can be adjusted, and the strength is improved; the stabilizer is added, so that the service life of the product is prolonged; adding a chain extender to adjust the crosslinking degree and strength of the polyether ester type polyurethane backrest; and a foaming agent and a catalyst are added, so that the performance of the backrest is improved.
The component B is added into the liquefied MDI to provide rigidity and strength for the material; the modified MDI is added to further improve the strength, tear resistance and other properties of the polyurethane. The proper weight ratio of liquefied MDI to modified MDI helps the backrest to balance between strength and tear resistance, which is also excellent while achieving higher strength.
Optionally, the polyether polyol A has a number average molecular weight of 600-5000, a functionality of 2-3 and a hydroxyl value of 20-40 mgKOH/g.
Through adopting above-mentioned technical scheme, the number average molecular weight range, the functionality range and the hydroxyl value range of this application polyether polyol A can make the back obtain higher intensity, processability, pliability and tear resistance. If the number average molecular weight, functionality, and hydroxyl number are low, the strength and tear resistance of the back rest may be affected; if the number average molecular weight is high, the processability of the backrest may be affected; if the functionality is high, the flexibility of the backrest may be affected; if the hydroxyl value is high, the backrest may be too fragile and poor in flexibility.
Optionally, the polyether polyol A has a number average molecular weight of 2000-3000, a functionality of 3 and a hydroxyl value of 25-30 mgKOH/g.
Alternatively, the polyester polyol B has a number average molecular weight of 1000 to 2000, a functionality of 2 and a hydroxyl value of 50 to 70mgKOH/g.
Through adopting above-mentioned technical scheme, the number average molecular weight scope, the functionality scope and the hydroxyl value scope of this application polyester polyol B can balance the intensity and the pliability of back, obtain higher tear resistance. If the number average molecular weight, functionality, and hydroxyl number are low, the strength and tear resistance of the backrest may be reduced; if the number average molecular weight is high, the processability of the backrest may be affected; if the functionality is high, the flexibility of the backrest may be affected; if the hydroxyl value is high, the backrest may be too fragile and poor in flexibility.
Optionally, the polyester polyol B has a number average molecular weight of 1500 to 1800, a functionality of 2 and a hydroxyl value of 55 to 65mgKOH/g.
Optionally, the stabilizer is at least one selected from polydimethylsiloxane, triphenyl phosphate and ethylene glycol dibenzoate;
the chain extender is at least one selected from 1, 4-butanediol and ethylene glycol;
the foaming agent is at least one selected from water and polystyrene microspheres;
the catalyst is at least one selected from dibutyl tin di (isooctyl thioglycollate), triethylene diamine and N, N-dimethylethanolamine.
Through adopting above-mentioned technical scheme, the stabilizer of this application selection can effectively restrain the oxidation reaction that the back received in processing and use, prevents ageing and degradation, increase of service life, can also improve the heat stability, ultraviolet resistance and the anti low temperature performance of back, prevents and treats back embrittlement, fracture.
The chain extender selected by the application can effectively adjust the strength and flexibility of the backrest, increase the ductility and improve the tear resistance and the durability.
The foaming agent selected by the application can reduce the density of the backrest, keep higher strength at the same time, and can also improve the impact resistance and buffering performance of the backrest.
The catalyst selected by the application can promote the polymerization reaction and improve the reaction rate, thereby improving the production efficiency of the backrest. By controlling the degree of polymerization, the strength and tear resistance of the backrest is improved.
Optionally, the modified MDI is polyethylene glycol modified MDI, wherein the polyethylene glycol modified MDI comprises polyethylene glycol and MDI for preparation, and the weight ratio of the polyethylene glycol to the MDI is 1:2-5.
Through adopting above-mentioned technical scheme, this application adopts polyethylene glycol modified MDI, and in the modified MDI that obtains added the B component, can improve the intensity of back, increase the pliability of material, improve tear resistance.
Optionally, the molecular weight of the polyethylene glycol is 600-1000.
By adopting the technical scheme, when the molecular weight of the polyethylene glycol is 600-1000, the hardness and toughness of the material can be balanced, and if the molecular weight is too low, the strength is high, the toughness is poor, and the tear resistance is poor; if the molecular weight is too high, the toughness is good and the strength is poor.
Optionally, the polyethylene glycol modified MDI is prepared as follows: mixing polyethylene glycol and MDI, and stirring for 0.5-1 h at the stirring speed of 200-300 r/min at the temperature of 50-80 ℃ to prepare the polyethylene glycol modified MDI.
By adopting the technical scheme, the preparation method of the polyethylene glycol modified MDI is simple to operate, low in energy consumption and environment-friendly.
In a second aspect, the present application provides a method for preparing the polyether ester polyurethane high-strength tear-resistant backrest, which comprises the following steps:
s1, mixing the polyether polyol A and the polyester polyol B, sequentially adding a stabilizer, a chain extender, a foaming agent and a catalyst, and stirring at room temperature for 1-2 hours at a stirring speed of 800-1000 r/min to obtain a component A;
s2, mixing the liquefied MDI with the modified MDI, and stirring for 0.5-1 h at a stirring speed of 60-80 r/min to obtain a component B;
s3, respectively injecting the component A and the component B into a foaming machine, mixing, foaming, pouring into a backrest mold, and curing to obtain the polyether ester type polyurethane high-strength tear-resistant backrest.
By adopting the technical scheme, the preparation method adopted by the application is simple and convenient to operate, and the preparation process is environment-friendly and pollution-free. The A, B components are separately mixed, the A component is sequentially added into the raw materials, the foaming performance of the polyether ester polyurethane is controlled, side reactions and adverse effects are avoided, and the prepared backrest is high in strength and high in tear resistance.
In the step S3, the backrest is manufactured through casting by a die, so that the gun-beating nail fixing process in the common backrest production procedure is omitted, the appearance of the product is attractive, the labor input is reduced, and the production efficiency is greatly improved.
Optionally, in the step S2, the liquefied MDI is in a nitrogen atmosphere when mixed with the modified MDI.
By adopting the technical scheme, when the B component is prepared, the B component is in the nitrogen atmosphere, so that oxygen in the air can be effectively removed, and oxidation reaction caused by contact of the oxygen with liquefied MDI and modified MDI is reduced. The interference of the water vapor on the B component can be reduced, and the influence of the water vapor on the mixing uniformity of the B component is avoided, so that the performance of the backrest is influenced.
Optionally, in the step S3, the foaming temperature is 100-150 ℃ and the foaming time is 5-10 min; the curing temperature is 25-45 ℃ and the curing time is 1-2 h.
By adopting the technical scheme, the technological parameters of the method can control the quality and performance of the backrest, and the high-strength and tear-resistant polyether ester polyurethane backrest product with high quality is prepared. If the foaming temperature is too low or the foaming time is too short, insufficient foaming may be caused; if the foaming temperature is too high or the foaming time is too long, excessive foaming may be caused, and the appearance of the product is rough.
If the curing temperature is too low or the curing time is too short, insufficient curing can be caused, the strength of the backrest is affected, and the problems of cracking and the like are caused; if the curing temperature is too high or the curing time is too long, the cost is increased and the production efficiency is reduced.
In a third aspect, the application provides application of the polyether ester type polyurethane high-strength tear-resistant backrest in the field of electric bicycles and motor cycle backrests.
Through adopting above-mentioned technical scheme, the high-strength tear-resistant back intensity of polyether ester formula polyurethane that this application made is high, tear resistance can be strong, in the application in electric bicycle and motorcycle back field, during production, cooperation dedicated mould structural design can remove the nail fixed process of beating in the ordinary back production process from, makes the product appearance pleasing to the eye to reduce the human input, improved production efficiency greatly.
In summary, the present invention includes at least one of the following beneficial technical effects:
1. the polyether ester type polyurethane high-strength tearing-resistant backrest is prepared by adopting specific raw materials and proportions and fully utilizing the comprehensive advantages of polyether type polyurethane materials and polyester type polyurethane materials, and has the advantages of high strength and high tearing resistance.
2. The component B is added into the liquefied MDI to provide rigidity and strength for the material; the modified MDI is added to further improve the strength, tear resistance and other properties of the polyurethane.
3. The preparation method is simple and convenient to operate, and environment-friendly and pollution-free in the preparation process. The A, B components are separately mixed, the A component is sequentially added into the raw materials, the foaming performance of the polyether ester polyurethane is controlled, side reactions and adverse effects are avoided, and the prepared backrest is high in strength and high in tear resistance.
4. The backrest is manufactured through die casting, the fixing process of the gun-striking nails in the common backrest production procedure is omitted, the appearance of the backrest is attractive, the labor input is reduced, and the production efficiency is greatly improved.
Detailed Description
The present application is described in further detail below with reference to examples.
The application designs a polyether ester type polyurethane high-strength tear-resistant backrest, which comprises an A component and a B component, wherein the weight ratio of the A component to the B component is 100: 60-70 parts;
the component A comprises 70-80 parts of polyether polyol A, 20-30 parts of polyester polyol B, 1-1.5 parts of stabilizer, 0.5-1 part of chain extender, 3-3.5 parts of foaming agent and 2-2.5 parts of catalyst;
the component B comprises liquefied MDI and modified MDI, and the weight ratio of the liquefied MDI to the modified MDI is 50-60: 40-50.
The polyether ester type polyurethane high-strength tear-resistant backrest is prepared by the following method, and comprises the following steps of:
s1, mixing the polyether polyol A and the polyester polyol B, sequentially adding a stabilizer, a chain extender, a foaming agent and a catalyst, and stirring at room temperature for 1-2 hours at a stirring speed of 800-1000 r/min to obtain a component A;
s2, mixing the liquefied MDI with the modified MDI, and stirring for 0.5-1 h at a stirring speed of 60-80 r/min to obtain a component B;
s3, respectively injecting the component A and the component B into a foaming machine, mixing, foaming, pouring into a backrest mold, and curing to obtain the polyether ester type polyurethane high-strength tear-resistant backrest.
The polyether ester type polyurethane high-strength tear-resistant backrest can be applied to the field of electric bicycles and motor cycle backrests.
The applicant designs the technical scheme of the application aiming at the problems that the existing backrest is relatively low in strength and easy to tear or deform.
The polyether ester type polyurethane high-strength tear-resistant backrest comprises a component A and a component B, wherein the component A comprises polyether polyol A, polyester polyol B, a stabilizer, a chain extender, a foaming agent and a catalyst, and the component B comprises liquefied MDI and modified MDI. The prepared polyether ester type polyurethane has high strength and tear resistance.
And secondly, the preparation method adopted by the application is simple and convenient to operate, and the preparation process is environment-friendly and pollution-free. The A, B components are separately mixed, the A component is sequentially added into the raw materials, the foaming performance of the polyether ester polyurethane is controlled, side reactions and adverse effects are avoided, and the prepared backrest is high in strength and high in tear resistance. The backrest is manufactured through die casting, the fixing process of the gun-striking nails in the common backrest production procedure is omitted, the appearance of the backrest is attractive, the labor input is reduced, and the production efficiency is greatly improved.
The raw materials adopted in the application are specifically as follows:
polydimethyl siloxane: CAS:9016-00-6.
Triphenyl phosphate: CAS:115-86-6.
Ethylene glycol dibenzoate: CAS:94-49-5.
1, 4-butanediol: CAS:110-63-4.
Ethylene glycol: CAS:107-21-1.
Polystyrene microspheres: CAS:9003-53-6.
Dibutyl tin bis (isooctyl thioglycolate): CAS:25168-24-5.
Triethylene diamine: CAS:280-57-9.
N, N-dimethylethanolamine: CAS:108-01-0.
Liquified MDI: wuhanpeng, a company of biotechnology, inc.
Polyethylene glycol: CAS:25322-68-3.
MDI：CAS：101-68-8。
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Examples 1 to 4
Example 1
The embodiment provides a polyether ester type polyurethane high-strength tear-resistant backrest, which comprises a component A and a component B, wherein the weight ratio of the component A to the component B is 100:65.
the component A comprises 75 parts of polyether polyol A, 25 parts of polyester polyol B, 1.2 parts of polydimethylsiloxane, 0.8 part of 1, 4-butanediol, 3.5 parts of water and 2.3 parts of dibutyltin bis (isooctylthio acetic acid) in parts by weight; the component B comprises the following components in percentage by weight: 40 and modified MDI.
The polyether polyol A had a number average molecular weight of 2500, a functionality of 3 and a hydroxyl value of 30mgKOH/g. The polyester polyol B had a number average molecular weight of 1500, a functionality of 2 and a hydroxyl value of 60mgKOH/g.
Preparation of modified MDI: the weight ratio is 1:3 and MDI at 65 ℃ at a stirring speed of 250r/min for 1h.
The preparation method comprises the following steps:
s1, mixing polyether polyol A and polyester polyol B, sequentially adding polydimethylsiloxane, 1, 4-butanediol, water and di (isooctyl thioglycollic acid) dibutyl tin, and stirring at a stirring speed of 900r/min for 1.5h at room temperature to obtain a component A; s2, mixing the liquefied MDI with the modified MDI, and stirring for 0.8h at a stirring speed of 70r/min to obtain a component B;
s3, respectively injecting the component A and the component B into a foaming machine, mixing and foaming for 8min at 125 ℃, pouring into a backrest mold, and curing for 1.5h at 35 ℃ to obtain the polyether ester type polyurethane high-strength tear-resistant backrest.
Example 2
The embodiment provides a polyether ester type polyurethane high-strength tear-resistant backrest, which comprises a component A and a component B, wherein the weight ratio of the component A to the component B is 100:70.
the component A comprises 78 parts of polyether polyol A, 20 parts of polyester polyol B, 1.5 parts of polydimethylsiloxane, 0.6 part of 1, 4-butanediol, 3.2 parts of water and 2 parts of dibutyltin bis (isooctylthio acetic acid) in parts by weight; the component B comprises the following components in percentage by weight: 40 and modified MDI.
The polyether polyol A had a number average molecular weight of 2500, a functionality of 3 and a hydroxyl value of 30mgKOH/g. The polyester polyol B had a number average molecular weight of 1500, a functionality of 2 and a hydroxyl value of 60mgKOH/g.
Preparation of modified MDI: the weight ratio is 1:3 and MDI at 65 ℃ at a stirring speed of 250r/min for 1h.
The preparation method comprises the following steps:
s1, mixing polyether polyol A and polyester polyol B, sequentially adding polydimethylsiloxane, 1, 4-butanediol, water and di (isooctyl thioglycollic acid) dibutyl tin, and stirring at a stirring speed of 950r/min for 1h at room temperature to obtain a component A;
s2, mixing the liquefied MDI with the modified MDI, and stirring for 0.6h at a stirring speed of 65r/min to obtain a component B;
s3, respectively injecting the component A and the component B into a foaming machine, mixing and foaming for 8min at 125 ℃, pouring into a backrest mold, and curing for 1.5h at 35 ℃ to obtain the polyether ester type polyurethane high-strength tear-resistant backrest.
Example 3
The embodiment provides a polyether ester type polyurethane high-strength tear-resistant backrest, which comprises a component A and a component B, wherein the weight ratio of the component A to the component B is 100:60.
the component A comprises 70 parts of polyether polyol A, 28 parts of polyester polyol B, 1.3 parts of polydimethylsiloxane, 0.5 part of 1, 4-butanediol, 3.4 parts of water and 2.5 parts of dibutyltin bis (isooctylthio acetic acid) in parts by weight; the component B comprises the following components in percentage by weight: 50 liquefied MDI and modified MDI.
The polyether polyol A had a number average molecular weight of 2500, a functionality of 3 and a hydroxyl value of 30mgKOH/g. The polyester polyol B had a number average molecular weight of 1500, a functionality of 2 and a hydroxyl value of 60mgKOH/g.
Preparation of modified MDI: the weight ratio is 1:3 and MDI at 65 ℃ at a stirring speed of 250r/min for 1h.
The preparation method comprises the following steps:
s1, mixing polyether polyol A and polyester polyol B, sequentially adding polydimethylsiloxane, 1, 4-butanediol, water and dibutyltin di (isooctylthio acetic acid), and stirring at room temperature for 2 hours at a stirring speed of 800r/min to obtain a component A;
s2, mixing the liquefied MDI with the modified MDI, and stirring for 1h at a stirring speed of 60r/min to obtain a component B;
s3, respectively injecting the component A and the component B into a foaming machine, mixing and foaming for 8min at 125 ℃, pouring into a backrest mold, and curing for 1.5h at 35 ℃ to obtain the polyether ester type polyurethane high-strength tear-resistant backrest.
Example 4
The embodiment provides a polyether ester type polyurethane high-strength tear-resistant backrest, which comprises a component A and a component B, wherein the weight ratio of the component A to the component B is 100:68.
the component A comprises 80 parts of polyether polyol A, 30 parts of polyester polyol B, 1 part of polydimethylsiloxane, 1 part of 1, 4-butanediol, 3 parts of water and 2.2 parts of dibutyltin di (isooctylthio acetic acid) in parts by weight; the component B comprises the following components in percentage by weight: 50 liquefied MDI and modified MDI.
The polyether polyol A had a number average molecular weight of 2500, a functionality of 3 and a hydroxyl value of 30mgKOH/g. The polyester polyol B had a number average molecular weight of 1500, a functionality of 2 and a hydroxyl value of 60mgKOH/g.
Preparation of modified MDI: the weight ratio is 1:3 and MDI at 65 ℃ at a stirring speed of 250r/min for 1h.
The preparation method comprises the following steps:
s1, mixing polyether polyol A and polyester polyol B, sequentially adding polydimethylsiloxane, 1, 4-butanediol, water and di (isooctyl thioglycollic acid) dibutyl tin, and stirring at a stirring speed of 1000r/min for 1.8h at room temperature to obtain a component A; s2, mixing the liquefied MDI with the modified MDI, and stirring for 0.5h at a stirring speed of 80r/min to obtain a component B;
s3, respectively injecting the component A and the component B into a foaming machine, mixing and foaming for 8min at 125 ℃, pouring into a backrest mold, and curing for 1.5h at 35 ℃ to obtain the polyether ester type polyurethane high-strength tear-resistant backrest.
Comparative examples 1 to 4
Comparative example 1
Comparative example 1 differs from example 1 in that in comparative example 1, the weight ratio of the a component and the B component is 100:80.
comparative example 2
Comparative example 2 differs from example 1 in that in comparative example 2, the weight ratio of the a component and the B component is 100:50.
comparative example 3
Comparative example 3 differs from example 1 in that comparative example 3 replaces the modified MDI in the B component with an equivalent amount of MDI.
Comparative example 4
Comparative example 4 differs from example 1 in that the preparation method of comparative example 4 is: mixing all the raw materials, stirring at 900r/min for 1.5h, injecting into foaming agent, foaming at 125deg.C for 8min, pouring into back mold, and solidifying at 35deg.C for 1.5h to obtain the final product.
Experimental detection
Detection item and detection method
According to GB/T531.1-2008 first part of the method for testing the indentation hardness of vulcanized rubber or thermoplastic rubber: shore hardness (A) of the high-strength tear-resistant backrest of the polyether ester polyurethane is measured by a Shore hardness meter method (Shore hardness).
The tensile strength of the polyether ester polyurethane high-strength tear-resistant backrest is measured according to GB/T528-2009 "measurement of tensile stress and strain properties of vulcanized rubber or thermoplastic rubber".
The tear strength of the polyether ester polyurethane high strength tear resistant back was determined according to GB/T529-2008 determination of tear strength of vulcanized rubber or thermoplastic rubber (trouser, right angle and crescent shaped samples).
The polyether ester polyurethane high-strength tear-resistant backrests prepared in examples 1 to 4 and comparative examples 1 to 4 were subjected to measurement of Shore hardness (A), tensile strength and tear strength, and the detection results are shown in Table 1.
TABLE 1
| Shore hardness (A) | Tensile Strength (MPa) | Tear Strength (kN/m) | |
| Example 1 | 76 | 24 | 97 |
| Example 2 | 73 | 21 | 92 |
| Example 3 | 71 | 20 | 90 |
| Example 4 | 74 | 22 | 95 |
| Comparative example 1 | 78 | 26 | 75 |
| Comparative example 2 | 66 | 18 | 91 |
| Comparative example 3 | 74 | 23 | 89 |
| Comparative example 4 | 69 | 19 | 88 |
From the test results shown in Table 1, it is understood that the polyether ester polyurethanes prepared in examples 1 to 4 have high strength, high hardness of the tear-resistant backrest, high tensile strength, high tear strength and excellent tear resistance.
The B component of comparative example 1 was too high in the ratio to give a backrest having high hardness and strength, but the tear strength was remarkably lowered and the processability was deteriorated.
The B component of comparative example 2 was too low in proportion, and the hardness and strength of the resulting backrest were significantly reduced.
Comparative example 3 the tear resistance of the resulting back was significantly reduced by replacing the modified MDI in the B component with an equivalent MDI.
Comparative example 4 the hardness, strength and tear resistance of the resulting back rest were all inferior to those of example 1 by blending all the materials together.
Examples 5 to 19
Example 5
Example 5 differs from example 1 in that in example 5, the polyether polyol A has a number average molecular weight of 600 and a hydroxyl value of 20mgKOH/g.
Example 6
Example 6 differs from example 1 in that in example 6, the polyether polyol A has a number average molecular weight of 5000 and a hydroxyl value of 40mgKOH/g.
Example 7
Example 7 differs from example 1 in that in example 7, the polyester polyol B has a number average molecular weight of 1000 and a hydroxyl value of 50mgKOH/g.
Example 8
Example 8 differs from example 1 in that in example 8, the polyester polyol B has a number average molecular weight of 2000 and a hydroxyl value of 70mgKOH/g.
Example 9
Example 9 differs from example 1 in that example 9 replaces 1.2 parts of polydimethylsiloxane with 0.4 parts of polydimethylsiloxane, 0.4 parts of triphenyl phosphate and 0.4 parts of ethylene glycol dibenzoate.
Example 10
Example 10 differs from example 9 in that example 10 replaces 0.8 part of 1, 4-butanediol with 0.4 part of 1, 4-butanediol and 0.4 part of ethylene glycol.
Example 11
Example 11 differs from example 1 in that example 11 replaces 3.5 parts of water with an equal weight of polystyrene microspheres.
Example 12
Example 12 differs from example 10 in that example 12 replaces 2.3 parts of dibutyltin bis (isooctylthio acetic acid) with 0.7 parts of dibutyltin bis (isooctylthio acetic acid), 0.8 parts of triethylenediamine and 0.8 parts of N, N-dimethylethanolamine.
Example 13
Example 13 differs from example 1 in that in example 13, the weight ratio of polyethylene glycol to MDI in the preparation of the modified MDI is 1:2.
example 14
Example 14 differs from example 1 in that in example 14, the weight ratio of polyethylene glycol to MDI in the preparation of the modified MDI is 1:5.
example 15
Example 15 differs from example 1 in that in step S2 of example 15, the liquefied MDI is mixed with the modified MDI without nitrogen atmosphere protection.
Example 16
Example 16 differs from example 1 in that in step S3 of example 16, the foaming temperature is 100 ℃ and the foaming time is 5min.
Example 17
Example 17 differs from example 1 in that in step S3 of example 17, the foaming temperature is 150 ℃ and the foaming time is 10min.
Example 18
Example 18 differs from example 1 in that in step S3 of example 18, the curing temperature is 25 ℃ and the curing time is 1h.
Example 19
Example 19 differs from example 1 in that in step S3 of example 19, the curing temperature is 45 ℃ and the curing time is 2h.
The polyether ester polyurethane high-strength tear-resistant backrest prepared in examples 5 to 19 was subjected to measurement of Shore hardness (A), tensile strength and tear strength, and the detection results are shown in Table 2.
TABLE 2
| Shore hardness (A) | Tensile Strength (MPa) | Tear Strength (kN/m) | |
| Example 5 | 73 | 22 | 94 |
| Example 6 | 77 | 25 | 91 |
| Example 7 | 72 | 22 | 93 |
| Example 8 | 77 | 24 | 92 |
| Example 9 | 78 | 25 | 98 |
| Example 10 | 79 | 26 | 99 |
| Example 11 | 75 | 23 | 96 |
| Example 12 | 79 | 27 | 99 |
| Example 13 | 73 | 22 | 94 |
| Example 14 | 75 | 23 | 95 |
| Example 15 | 67 | 19 | 85 |
| Example 16 | 70 | 21 | 88 |
| Example 17 | 75 | 24 | 95 |
| Example 18 | 72 | 22 | 90 |
| Example 19 | 76 | 24 | 97 |
From the test results shown in Table 2, the polyether ester polyurethane prepared in example 5 and example 7 had reduced strength and tear resistance of the high strength tear resistant backrest. The polyether ester polyurethane high strength tear resistant backrests prepared in examples 6 and 8 have less variation in hardness and tensile strength, but have reduced tear resistance and poor processability during processing.
The polyether ester polyurethane prepared in example 9 has better strength and tear resistance than those of example 1. The polyether ester polyurethane prepared in example 10 has better strength and tear resistance than the polyether ester polyurethane prepared in example 9.
In example 11, polystyrene microspheres are used as a foaming agent, and the strength and tear resistance of the prepared polyether ester polyurethane high-strength tear-resistant backrest are lower than those of example 1.
The polyether ester polyurethane high strength tear resistant backrest prepared in example 12 is stronger than example 10.
The polyether ester polyurethane high strength tear resistant backrests prepared in examples 13 and 14 are less strong and less resistant to tearing than example 1.
The polyether ester polyurethane prepared in example 15 has significantly reduced strength and tear resistance of the high strength tear back.
The polyether ester polyurethane high strength tear resistant backrests prepared in example 16 and example 18 are less strong and less resistant to tearing than example 1.
The polyether ester polyurethane high-strength tear-resistant backrest prepared in the example 17 and the example 19 has the strength and tear resistance similar to those of the example 1, but has higher energy consumption, longer time and low production efficiency.
The foregoing are all preferred embodiments of the present application, and are not intended to limit the scope of the present application in any way, therefore: all equivalent changes in structure, shape and principle of this application should be covered in the protection scope of this application.
Claims (10)
1. The polyether ester type polyurethane high-strength tear-resistant backrest is characterized by comprising a component A and a component B, wherein the weight ratio of the component A to the component B is 100: 60-70 parts;
the component A comprises, by weight, 70-80 parts of polyether polyol A, 20-30 parts of polyester polyol B, 1-1.5 parts of a stabilizer, 0.5-1 part of a chain extender, 3-3.5 parts of a foaming agent and 2-2.5 parts of a catalyst;
the component B comprises liquefied MDI and modified MDI, and the weight ratio of the liquefied MDI to the modified MDI is 50-60: 40-50.
2. The polyether ester polyurethane high strength tear resistant backrest of claim 1, wherein the polyether polyol a has a number average molecular weight of 600 to 5000, a functionality of 2 to 3, and a hydroxyl value of 20 to 40mgkoh/g.
3. The polyether ester polyurethane high-strength tear-resistant backrest of claim 1, wherein the polyester polyol B has a number average molecular weight of 1000-2000, a functionality of 2 and a hydroxyl value of 50-70 mgkoh/g.
4. The polyether ester polyurethane high strength tear resistant backrest of claim 1, wherein the stabilizer is selected from at least one of polydimethylsiloxane, triphenyl phosphate, ethylene glycol dibenzoate;
the chain extender is at least one selected from 1, 4-butanediol and ethylene glycol;
the foaming agent is at least one selected from water and polystyrene microspheres;
the catalyst is at least one selected from dibutyl tin di (isooctyl thioglycollate), triethylene diamine and N, N-dimethylethanolamine.
5. The polyether ester polyurethane high strength tear resistant backrest of claim 1, wherein the modified MDI is polyethylene glycol modified MDI, the polyethylene glycol modified MDI is prepared from polyethylene glycol and MDI in a weight ratio of 1:2-5.
6. The polyetherester polyurethane high strength tear resistant backrest of claim 5, wherein the polyethylene glycol modified MDI is prepared by: and mixing polyethylene glycol and MDI, and stirring at the stirring speed of 200-300 r/min for 0.5-1 h at the temperature of 50-80 ℃ to obtain the polyethylene glycol modified MDI.
7. A method for preparing the polyether ester polyurethane high-strength tear-resistant backrest of claim 1, which is characterized by comprising the following steps:
s1, mixing polyether polyol A and polyester polyol B, sequentially adding a stabilizer, a chain extender, a foaming agent and a catalyst, and stirring at room temperature at a stirring speed of 800-1000 r/min for 1-2 h to obtain a component A;
s2, mixing the liquefied MDI with the modified MDI, and stirring for 0.5-1 h at a stirring speed of 60-80 r/min to obtain a component B;
s3, respectively injecting the component A and the component B into a foaming machine, mixing, foaming, pouring into a backrest mold, and curing to obtain the polyether ester type polyurethane high-strength tear-resistant backrest.
8. The method for preparing a high-strength tear-resistant backrest of polyether ester polyurethane according to claim 7, wherein in the step S2, the liquefied MDI is in a nitrogen atmosphere when mixed with the modified MDI.
9. The method for preparing the polyether ester polyurethane high-strength tear-resistant backrest according to claim 7, wherein in the step S3, the foaming temperature is 100-150 ℃ and the foaming time is 5-10 min; the curing temperature is 25-45 ℃, and the curing time is 1-2 hours.
10. Use of the polyether ester polyurethane high-strength tear-resistant backrest according to any one of claims 1 to 6 in the field of electric bicycles and motorcycles.
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