CN108003323B - Shock-absorbing energy-absorbing polyurethane material and preparation method thereof - Google Patents
Shock-absorbing energy-absorbing polyurethane material and preparation method thereof Download PDFInfo
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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
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- C08G18/30—Low-molecular-weight compounds
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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
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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
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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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- C08G2110/00—Foam properties
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- C08G2110/0066—≥ 150kg/m3
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Abstract
The invention provides a shock-absorbing and energy-absorbing polyurethane material and a preparation method thereof, wherein the polyurethane material is obtained by reacting raw materials containing an A isocyanate reactive component and a B isocyanate component, wherein the A isocyanate reactive component comprises the following components in parts by weight: a1 polyol component, a2 blowing agent, A3 catalyst; wherein the A1 polyalcohol component contains no less than 50% of bio-based polyalcohol by mass; the prepared polyurethane material has good damping and energy absorbing effects, excellent comprehensive performance and environmental protection. The preparation method is simple and easy to implement.
Description
Technical Field
The invention relates to a shock-absorbing and energy-absorbing polyurethane material, in particular to a bio-based shock-absorbing and energy-absorbing polyurethane material, and a preparation method and application of the material.
Background
With the continuous development of modern society, people pay more and more attention to the harm caused by vibration and noise, and the vibration and the noise not only harm the physical and mental health of human beings, but also cause the damage of mechanical equipment, instrument pipelines and the like. In order to eliminate the adverse effects caused by vibration and noise, various control technical means must be adopted, wherein the most widely used and effective method is to use high-damping shock absorption materials.
The high damping shock absorbing material is generally a polymer material, and has dual properties of elasticity and viscosity, which are determined by the molecular structure characteristics of the polymer material. The damping of the material is high, vibration can be greatly attenuated, the larger the damping is, the smaller the resonance amplitude is, namely, the loss factor (tan value) of the material is larger, the better the viscosity of the material is, and the better the damping effect is. However, the material has a certain mechanical strength while maintaining a good damping effect, and therefore, the loss factor of the material should be in a proper range.
The polyurethane material is used as a common damping and energy-absorbing material, has proper viscoelasticity and is widely applied, but the traditional polyurethane material is prepared by reacting petroleum-based polyether or polyester polyol with isocyanate, the environmental pollution is increased along with the continuous reduction of petroleum/petrochemical resources, and the renewable biomass resources are gradually paid attention and developed to replace the petroleum-based polyol.
The patent CN201611225743.4 discloses a polyurethane damping material and a preparation method thereof, the method is a polyurethane mixing process, the process is relatively complex, the mixing temperature at least needs to be more than 150 ℃, and the energy consumption is large.
Patent CN201280025606.X discloses a high resilience polyurethane foam containing castor oil, the usage amount of castor oil in the invention is up to 30%, the degradable components are less, and the environmental protection property can be further improved.
Therefore, a material with high content of bio-based components, good shock absorption and energy absorption effects and excellent comprehensive performance needs to be provided to solve the problems in the prior art.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a polyurethane material with high content of bio-based components, good damping and energy absorbing effects and excellent comprehensive performance, and a preparation method of the polyurethane material.
In order to solve the above technical problems, the technical solution of the present invention is as follows.
A shock-absorbing and energy-absorbing polyurethane material is obtained by reacting raw materials comprising an A isocyanate reactive component and a B isocyanate component, wherein the A isocyanate reactive component comprises: a1 polyol component, a2 blowing agent, A3 catalyst;
wherein the A1 polyol component comprises bio-based polyols in an amount of greater than or equal to 50%, preferably greater than or equal to 85%, more preferably equal to 100%, based on the total mass of the A1 polyol component.
The bio-based polyol of the present invention refers to a natural compound containing a hydroxyl group, or an isolate of the natural compound, or a derivative of the natural compound, which may be used alone or in combination. Examples of biobased polyols that may be cited include, but are not limited to, castor oil, soybean oil, sunflower oil, rapeseed oil, linseed oil, cottonseed oil, tung oil, palm oil, poppy seed oil, corn oil, peanut oil, and the like, as well as isolates or derivatives thereof. Such substances may be used alone or in combination.
As a preferred technical scheme of the invention, the bio-based polyol is castor oil.
When the content of the bio-based polyol in the a1 polyol component is not 100%, the remainder is other polyols than the bio-based polyol, and the other polyols may be selected from polyols commonly used in the art, such as polyether polyol, polyester polyol, polycarbonate polyol, and the like, and such polyols may be used alone or in combination.
The NCO content of the isocyanate component B is 18-33 wt%, and preferably 22-32 wt%.
The B isocyanate component may be selected from any organic isocyanate commonly used in the art, examples of which include, but are not limited to, Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polyphenylmethane Polyisocyanate (PMDI), 1, 5-Naphthalene Diisocyanate (NDI), Hexamethylene Diisocyanate (HDI), methylcyclohexyl diisocyanate, 4' -dicyclohexylmethane diisocyanate, isophorone diisocyanate (IPDI), p-phenylene diisocyanate (PPDI), p-phenylene diisocyanate (XDI), tetramethyldimethylene diisocyanate (TMXDI), and the like, and derivatives of such isocyanates. The above organic isocyanates may be used alone or in combination. The B isocyanate component is available commercially or may be prepared by methods commonly used in the art.
As a preferred embodiment of the present invention, the B isocyanate component comprises:
b1 urethane-modified isocyanate accounting for 40-100%, preferably 60-85% of the total mass of the B isocyanate component;
b2 toluene diisocyanate, which accounts for 0-20%, preferably 5-10% of the total mass of the B isocyanate component;
b3 carbodiimide modified isocyanate, which accounts for 0-40%, preferably 5-30% of the total mass of the isocyanate component B;
the B4 polymethylene polyphenyl polyisocyanate accounts for 0-30% of the total mass of the B isocyanate component, and preferably 5-15%.
The B1 urethane-modified isocyanate, B2 toluene diisocyanate, B3 carbodiimide-modified isocyanate and B4 polymethylene polyphenyl polyisocyanate can be obtained from commercial sources or prepared by methods well known in the art.
In a preferred embodiment of the invention, the B1 urethane-modified isocyanate is obtained by reacting B11 polyol and B12 isocyanate.
The B11 polyol may be selected from polyols commonly used in the art, such as polyether polyols, polyester polyols, polyether carbonate polyols, small molecule alcohols, and the like, and such polyols may be used alone or in combination. Other polyols commonly used in the art may also be used in the present invention.
In a preferred embodiment of the present invention, the B11 polyol is a polyether polyol having a number average molecular weight of 50 to 10000 and an average functionality of 2 to 4.
The B12 isocyanate may be selected from any organic isocyanate commonly used in the art, examples of which include, but are not limited to, Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polyphenylmethane Polyisocyanate (PMDI), 1, 5-Naphthalene Diisocyanate (NDI), Hexamethylene Diisocyanate (HDI), methylcyclohexyl diisocyanate, 4' -dicyclohexylmethane diisocyanate, isophorone diisocyanate (IPDI), p-phenylene diisocyanate (PPDI), p-phenylene diisocyanate (XDI), tetramethyldimethylene diisocyanate (TMXDI), and the like, and polymers of such isocyanates. The above organic isocyanates may be used alone or in combination. The B12 isocyanate is available commercially or may be prepared by methods commonly used in the art.
In a preferred embodiment of the present invention, the isocyanate B12 is diphenylmethane diisocyanate.
It should be noted that any organic isocyanate described in the present invention, which contains any isomer or mixture of isomers, does not affect the practice of the present invention.
In a preferred embodiment of the present invention, the B12 isocyanate is a mixture of diphenylmethane-4, 4 '-diisocyanate and diphenylmethane-2, 4-diisocyanate, wherein the diphenylmethane-4, 4' -diisocyanate accounts for 80 to 100%, preferably 90 to 100%, of the total mass of the B12 isocyanate.
In a preferred embodiment of the present invention, B13 chain extender is further used in the preparation of the B1 urethane-modified isocyanate, the B13 chain extender may be a chain extender commonly used in the art, and examples include, but are not limited to, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, cyclohexanediol, hydrogenated bisphenol a, and the like, and such chain extenders may be used alone or in combination.
In the preparation of the B1 urethane-modified isocyanate, parameters, processes, steps and the like which are not described can be carried out according to a method commonly used in the field, and the implementation of the invention is not influenced.
The blowing agent A2 may be selected from chemical or physical blowing agents commonly used in the art, and examples that may be cited include, but are not limited to, water, chlorodifluoromethane, monochloromonofluoromethane, dichlorodifluoromethane, trichlorofluoromethane, butane, pentane, cyclopentane, hexane, cyclohexane, heptane, air, CO2、N2And the like, such blowing agents may be used alone or in combination. Preferably, the a2 foaming agent is water.
The a3 catalyst may be selected from catalysts commonly used in the art, such as amine-based catalysts, organometallic-based catalysts, and the like, and examples thereof include, but are not limited to, bis (dimethylaminoethyl) ether, triethylamine, tributylamine, triethylenediamine, dimethylethanolamine, N-ethylmorpholine, N' -tetramethyl-ethylenediamine, pentamethyldiethylenetriamine, N-methylaniline, N-dimethylaniline, tin (II) acetate, tin (II) octoate, tin ethylhexanoate, tin laurate, dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin maleate, dioctyltin diacetate, and the like, and such catalysts may be used alone or in combination.
The a isocyanate-reactive component further comprises a4 chain extender, the a4 chain extender can be a chain extender commonly used in the art, and examples thereof include, but are not limited to, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, cyclohexanediol, hydrogenated bisphenol a, and the like, and such chain extenders can be used alone or in combination.
The A isocyanate reactive component also comprises an A5 surfactant, the A5 surfactant can adopt surfactants commonly used in the field, and the listed examples include but are not limited to polysiloxane-oxyalkylene block copolymer and the like, and the surfactants can be used singly or in combination. In a preferred embodiment of the present invention, the A isocyanate-reactive component may be free of surfactants.
The A isocyanate-reactive component also contains A6 filler, and examples that may be cited include, but are not limited to, talc, diatomaceous earth, titanium dioxide, silica fume, calcium carbonate, and the like, which fillers may be used alone or in combination.
Other additives commonly used in the art may also optionally be used in the present invention, examples of which include, but are not limited to, flame retardants, coupling agents, smoke suppressants, pigments, antistatic agents, antioxidants, UV stabilizers, diluents, surface wetting agents, leveling agents, thixotropic agents, plasticizers, and the like.
Except for the specific description of the invention, the mass proportions of the components in the invention, which are not described, can be configured by referring to the mass proportions commonly used in the field, and the commonly used mass proportion configuration does not influence the implementation of the invention.
There is illustrated a preferred mass ratio of the components in the a isocyanate-reactive component of the present invention, the a isocyanate-reactive component comprising:
an A1 polyol component in an amount of 82-95%, preferably 85-94%, based on the total mass of the A isocyanate-reactive component;
an A2 foaming agent, the dosage of which is 0.2-2%, preferably 0.25-1.2%, based on the total mass of the A isocyanate reactive component;
the A3 catalyst is used in an amount of 1-5%, preferably 1.5-3%, based on the total mass of the A isocyanate reactive component;
the amount of the A4 chain extender is 0-10%, preferably 0.5-5%, based on the total mass of the A isocyanate reactive component;
the A5 surfactant is used in an amount of 0-2%, preferably 0-1%, based on the total mass of the A isocyanate reactive component;
the A6 filler is used in an amount of 0-10%, preferably 0-5%, based on the total mass of the A isocyanate-reactive component.
The molar ratio of reactive hydrogen atoms in the isocyanate reactive component A to NCO groups in the isocyanate component B is 1: 0.8-1.05; preferably 1: 0.85-0.95.
The density of the shock-absorbing and energy-absorbing polyurethane material is 50-500 kg/m3Preferably 120 to 400kg/m3(ii) a The ASKERC hardness is 5-65, preferably 20-50; the rebound resilience is 0.5-10%, preferably 0.5-6% according to the GB/T6670 plus 2008 standard test; the compression set is 0.2 to 10%, preferably 0.2 to 5%, as measured according to ASTM D-395-B.
The preparation method of the shock-absorbing and energy-absorbing polyurethane material comprises the steps of uniformly mixing an isocyanate reactive component A and an isocyanate component B for reaction, and obtaining the material after the reaction is finished.
It should be noted that parameters, processes, steps and the like which are not provided by the preparation method provided by the invention can be performed according to methods commonly used in the art, and the implementation of the invention is not affected. The preparation method aims to uniformly mix all the components for foaming reaction, all the components can be mixed at the same time for reaction, or the components which do not react with each other are mixed for reaction step by step, and then the mixtures are mixed for reaction, and the different mixing steps can ensure the smooth implementation of the invention, but the B1 urethane modified isocyanate is prepared or purchased before mixing.
In a preferred embodiment of the present invention, the preparation method comprises the steps of:
and (2) adding the isocyanate reactive component A and the isocyanate component B into a reactor at the same time, uniformly mixing and reacting, and obtaining the material after the reaction is finished, wherein the polyurethane modified isocyanate B1 is prepared before being added into the reactor.
In another preferred embodiment of the present invention, the preparation method comprises the steps of:
1) preparation of the isocyanate-reactive component: controlling the mixing temperature to be 20-60 ℃, preferably 35-55 ℃, and uniformly mixing the components to obtain an isocyanate reactive component A;
2) b preparation of the isocyanate component: uniformly mixing B11 polyol and B12 isocyanate in a reactor for reaction, controlling the temperature to be 60-90 ℃, preferably 75-85 ℃, and obtaining B1 urethane modified isocyanate after the reaction is finished;
controlling the temperature of the reactor to be 40-60 ℃, preferably 45-55 ℃, adding the rest components, and uniformly mixing to obtain an isocyanate component B;
3) and uniformly mixing the isocyanate reactive component A and the isocyanate component B for reaction, and obtaining the shock-absorbing and energy-absorbing polyurethane material after the reaction is finished.
It is to be noted that "each component" described in step 1) refers to each component contained in the a isocyanate-reactive component; the "remaining components" described in step 2) refer to the remaining components in the B isocyanate component.
The shock-absorbing and energy-absorbing polyurethane material can be used in any field meeting the requirements of mechanical properties and/or functionality, including but not limited to vehicles, buildings, household appliances, electronics, shoe materials, pipelines, homes and the like, and more specific application examples include but are not limited to vehicle seats or sound-insulating and shock-absorbing parts, building heat-insulating or sound-insulating materials, household appliance heat-insulating or shock-absorbing materials, electronic product shock-absorbing materials, shoe material midsoles or insoles, pipeline heat-insulating or shock-absorbing materials, pillows, mattresses and the like.
The invention has the beneficial effects that: the consumption of the bio-based polyol in the raw materials is high, and the raw materials are environment-friendly and renewable. The prepared polyurethane material has excellent mechanical property and shock absorption and energy absorption effects. The preparation method is simple, convenient and easy to implement, and is energy-saving and environment-friendly.
The specific implementation mode is as follows:
the present invention will be further described with reference to the following examples.
The raw materials of the examples and comparative examples include:
polyol 1: castor oil, produced by Tongliao Castor chemical Co., Ltd;
polyol 2: the modified polyether polyol is prepared by the steps of starting with glycerol, copolymerizing and grafting styrene and acrylonitrile, wherein the polyether polyol has the solid content of 30 percent, the content of ethylene oxide of 12 percent, the molecular weight of 6000, the functionality of 3 and the hydroxyl value of 28.1 mgKOH/g;
polyol 3: propylene glycol start, propylene oxide homopolymerization, molecular weight 2000, functionality 2, hydroxyl value 56 mgKOH/g;
polyol 4: starting with glycerol, copolymerizing ethylene oxide and propylene oxide, wherein the ethylene oxide content is 14%, the molecular weight is 4800, the functionality is 3, and the hydroxyl value is 35.1 mgKOH/g;
polyol 5: mixing glycerol and pentaerythritol, wherein the functionality is 3.4, ethylene oxide and propylene oxide are copolymerized, the ethylene oxide content is 15%, the molecular weight is 4000, the functionality is 3.4, and the hydroxyl value is 47.7 mgKOH/g;
polyol 6: glycerol initiation, ethylene oxide and propylene oxide copolymerization, molecular weight 8000, functionality 3, hydroxyl value 21.0 mgKOH/g;
a blowing agent, water;
chain extender: ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, dipropylene glycol, diethylene glycol;
catalyst: bis (dimethylaminoethyl) ether, triethylenediamine, dimethylcyclohexylamine, dimethylethanolamine;
surfactant (b): DC3043, manufactured by american gas company;
inorganic filler: talc powder, diatomaceous earth;
color paste: black paste, produced by Guangzhou Aike New materials Co., Ltd;
diphenylmethane diisocyanate: MDI-100; wherein the content of the diphenylmethane-4, 4' -diisocyanate is 99 percent by weight, and the production is realized by Wanhua chemistry;
toluene diisocyanate: TDI-80, Vanhua chemical production;
carbodiimide-modified isocyanate: CDMDI100L, wanhua chemical production;
polymethylene polyphenyl diisocyanate: PM-200, Wanhua chemical production.
B1 component, B2 component, B3 component, B4 component and B5 component were prepared according to the kinds and contents of the components in Table 1:
1. adding MDI-100 into a three-mouth bottle provided with a stirrer and a thermometer, heating to 80 ℃, adding polyol and a chain extender, and stirring at the speed of 80 revolutions per minute for 2 hours;
2. controlling the temperature of the mixture at 50 ℃, adding toluene diisocyanate, carbodiimide modified isocyanate and polymethylene polyphenyl polyisocyanate, and stirring for 0.5 hour.
Wherein the components not added in table 1 were not added in the above preparation method.
TABLE 1
| Categories | B1 component | B2 component | B3 component | B4 component | B5 component |
| MDI-100 (parts by mass) | 635 | 420 | 700 | 600 | |
| CDMDI100L (parts by mass) | 290 | 85 | 100 | ||
| TDI-80 (parts by mass) | 50 | 100 | 50 | ||
| PM200 (parts by mass) | 50 | 1000 | |||
| Polyol2 (parts by mass) | 290 | ||||
| Polyol3 (parts by mass) | 65 | ||||
| Polyol4 (parts by mass) | 100 | ||||
| Polyol5 (parts by mass) | 25 | 100 | |||
| Polyol6 (parts by mass) | 100 | 190 | |||
| Dipropylene glycol (parts by mass) | 40 | ||||
| 1, 3-propanediol (parts by mass) | 10 | ||||
| NCO content | 32wt％ | 18wt％ | 27wt％ | 22wt％ | 31wt％ |
Examples and comparative examples preparation methods: adding the component A raw material into a reactor according to the types and contents of the components in the table 2, uniformly stirring, controlling the temperature of the raw material at 40 ℃, adding the component A and the component B into a low-pressure machine, mixing, pouring into a mold at the temperature of 50 ℃, curing for 6 minutes, and then opening the mold to obtain the shock-absorbing and energy-absorbing polyurethane material.
TABLE 2 (in parts by mass)
The polyurethane materials prepared in examples and comparative examples were tested for mechanical properties after being left at room temperature for 30 hours.
The properties and test criteria of the polyurethane materials of the examples and comparative examples are shown in Table 3
TABLE 3
Claims (16)
1. The shock-absorbing and energy-absorbing polyurethane material is obtained by reacting raw materials comprising an A isocyanate reactive component and a B isocyanate component, wherein the A isocyanate reactive component comprises: a1 polyol component, a2 blowing agent, A3 catalyst;
wherein the A1 polyol component comprises castor oil, the castor oil content is greater than or equal to 85% and is not 100%, based on the total mass of the A1 polyol component;
the B isocyanate component comprises:
b1 urethane-modified isocyanate accounting for 40-100% of the total mass of the B isocyanate component;
b2 toluene diisocyanate, which accounts for 0-20% of the total mass of the B isocyanate component;
b3 carbodiimide modified isocyanate, which accounts for 0-40% of the total mass of the isocyanate component B;
and B4 polymethylene polyphenyl polyisocyanate accounts for 0-30% of the total mass of the B isocyanate component.
2. The polyurethane material of claim 1, wherein the NCO content of the B isocyanate component is 18-33 wt.%.
3. The polyurethane material of claim 1, wherein the NCO content of the B isocyanate component is 22-32 wt.%.
4. A polyurethane material as claimed in claim 1, wherein the B isocyanate component comprises:
b1 urethane-modified isocyanate accounting for 60-85% of the total mass of the B isocyanate component;
b2 toluene diisocyanate, which accounts for 5-10% of the total mass of the B isocyanate component;
b3 carbodiimide modified isocyanate accounting for 5-30% of the total mass of the isocyanate component B;
and B4 polymethylene polyphenyl polyisocyanate accounts for 5-15% of the total mass of the B isocyanate component.
5. The polyurethane material of claim 1, wherein the B1 urethane-modified isocyanate is obtained from the reaction of a B11 polyol and a B12 isocyanate.
6. The polyurethane material as claimed in claim 5, wherein the B11 polyol is a polyether polyol having a number average molecular weight of 50 to 10000 and an average functionality of 2 to 4;
the B12 isocyanate is diphenylmethane diisocyanate.
7. The polyurethane material as claimed in any one of claims 1 and 4 to 6, wherein a B13 chain extender is further used in the preparation process of the B1 urethane-modified isocyanate.
8. The polyurethane material of claim 1, wherein the A2 blowing agent is selected from the group consisting of water, chlorodifluoromethane, chlorofluoromethane, dichlorodifluoromethane, trichlorofluoromethane, butane, pentane, cyclopentane, hexane, cyclohexane, heptane, air, CO2And N2One or more of (a).
9. The polyurethane material of claim 1, wherein the a2 blowing agent is water.
10. A polyurethane material as claimed in claim 1, wherein the a isocyanate-reactive component further comprises a4 chain extender;
the A isocyanate reactive component also comprises an A5 surfactant;
the A isocyanate-reactive component also includes an A6 filler.
11. A polyurethane material as claimed in claim 10, wherein the a4 chain extender is selected from one or more of ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, cyclohexanediol and hydrogenated bisphenol a.
12. A polyurethane material as claimed in any one of claims 1, 8 and 10, wherein said a isocyanate-reactive component comprises:
an A1 polyol component, the usage amount of which is 82-95% based on the total mass of the A isocyanate reactive component;
an A2 foaming agent, the dosage of which is 0.2-2% of the total mass of the A isocyanate reactive component;
the catalyst A3, the dosage of which is 1-5% by total mass of the isocyanate reactive component A;
the amount of the A4 chain extender is 0-10% based on the total mass of the A isocyanate reactive component;
the amount of the A5 surfactant is 0-2% by total mass of the A isocyanate reactive component;
the filler A6, the amount of which is 0-10% by mass based on the total mass of the isocyanate reactive component A.
13. A polyurethane material as claimed in claim 12, wherein the a isocyanate-reactive component comprises:
the A1 polyol component is used in an amount of 85-94% by mass based on the total mass of the A isocyanate reactive component;
an A2 foaming agent, the dosage of which is 0.25-1.2% by total mass of the A isocyanate reactive component;
the catalyst A3, the dosage of which is 1.5-3% by total mass of the isocyanate reactive component A;
the amount of the A4 chain extender is 0.5-5% of the total mass of the A isocyanate reactive component;
the amount of the A5 surfactant is 0-1% by total mass of the A isocyanate reactive component;
the filler A6, the amount of which is 0-5% by mass based on the total mass of the isocyanate reactive component A.
14. The polyurethane material of claim 1, wherein the molar ratio of the reactive hydrogen atoms in the a isocyanate-reactive component to the NCO groups in the B isocyanate component is from 1:0.8 to 1.05.
15. The polyurethane material of claim 1, wherein the molar ratio of the reactive hydrogen atoms in the A isocyanate-reactive component to the NCO groups in the B isocyanate-reactive component is from 1:0.85 to 0.95.
16. A preparation method of the polyurethane material as claimed in any one of claims 1 to 15, characterized in that the material is obtained by uniformly mixing the isocyanate reactive component A and the isocyanate component B for reaction.
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| CN113248679A (en) * | 2020-07-02 | 2021-08-13 | 王聪 | Novel non-Newtonian polyurethane energy-absorbing buffer material and method for manufacturing insole by using same |
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| CN112920377B (en) * | 2021-01-29 | 2022-08-30 | 青岛海力威新材料科技股份有限公司 | Polyurethane soft foam material for railway solidified track bed and preparation method thereof |
| CN116606419A (en) * | 2023-04-12 | 2023-08-18 | 广东豪美新材股份有限公司 | Filling core body for energy absorption box |
| CN116675830A (en) * | 2023-04-24 | 2023-09-01 | 广东豪美新材股份有限公司 | Buffering energy-absorbing material |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1112941A (en) * | 1995-03-24 | 1995-12-06 | 埃勒夫阿托化学有限公司 | Polyaminoester elastic body composition with good buffering characterastic main composition of which are polydiallyl polyhydric alcohol and castor oil |
| CN1982352A (en) * | 2005-12-15 | 2007-06-20 | 上海凯众聚氨酯有限公司 | Production of MDI-polyurethane microporous elastomer |
| WO2008003567A1 (en) * | 2006-07-04 | 2008-01-10 | Huntsman International Llc | Process for making visco-elastic foams |
| CN101948616A (en) * | 2010-09-13 | 2011-01-19 | 安徽大学 | Microporous polyurethane elastomer shock absorption element for high-speed railway and preparation method thereof |
| CN102159610A (en) * | 2008-07-18 | 2011-08-17 | 陶氏环球技术有限责任公司 | Natural resource based viscoelastic foams |
| CN106632962A (en) * | 2016-11-08 | 2017-05-10 | 佛山林至高分子材料科技有限公司 | Plant oil-based cartilage bionic buffer damping material and preparation method and application thereof |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE388177T1 (en) * | 2003-04-25 | 2008-03-15 | Dow Global Technologies Inc | VEGETABLE OIL BASED POLYOLS AND METHOD FOR THE PRODUCTION THEREOF |
| CN1247656C (en) * | 2003-08-07 | 2006-03-29 | 烟台万华聚氨酯股份有限公司 | Production process and use of polyester polyol and its modifying material |
| CN101238162B (en) * | 2005-08-12 | 2011-07-06 | 三井化学株式会社 | Composition for polyurethane foam, polyurethane foam obtained from the composition, and use thereof |
| BRPI0600782A (en) * | 2006-02-24 | 2007-11-20 | Phb Ind Sa | composition for preparing degradable polyester polyol, process for obtaining polyester, elastomer, foam, paint and adhesive polyols, and degradable foam of a polyester polyol |
| US20070238798A1 (en) * | 2006-04-05 | 2007-10-11 | Mcdaniel Kenneth G | Flexible polyurethane foams made from vegetable oil alkoxylated via DMC-catalysis |
| EP2176312A1 (en) * | 2007-08-06 | 2010-04-21 | Dow Global Technologies Inc. | Polyol blends and their use in making polymers |
| CN101503502B (en) * | 2008-02-04 | 2012-03-28 | 上海巨安科技有限公司 | Thermoplastic hard polyurethane foam plastic and preparation thereof |
| CA2796656C (en) * | 2010-04-23 | 2018-07-03 | Bayer Materialscience Llc | Polyols suitable for hot molded foam production with high renewable resource content |
| US9035105B2 (en) * | 2012-07-20 | 2015-05-19 | Bayer Materialscience Llc | Process for the in situ production of polyether polyols based on renewable materials and their use in the production of flexible polyurethane foams |
| CN102786658B (en) * | 2012-08-23 | 2014-03-05 | 山东一诺威聚氨酯股份有限公司 | Polyurethane composition for jogging area of plastic venue and preparation method thereof |
| CN103601866B (en) * | 2013-11-26 | 2015-11-04 | 北京联合大学生物化学工程学院 | A kind of method utilizing plant polyatomic alcohol synthesis of polyurethane foam materials |
| CN103626948B (en) * | 2013-11-26 | 2016-06-08 | 北京联合大学生物化学工程学院 | A kind of polyurethane foamed material utilizing plant polyatomic alcohol to synthesize |
| CN107151302B (en) * | 2016-03-03 | 2020-08-11 | 中国石油化工股份有限公司 | Vegetable oil-based soft polyurethane foam plastic and preparation method thereof |
| CN105968292A (en) * | 2016-04-26 | 2016-09-28 | 天津科技大学 | Cassava residue based polyols and cassava residue based polyurethane foam plastics, and preparation methods and applications thereof |
| CN106560480A (en) * | 2016-08-03 | 2017-04-12 | 广州艾科新材料股份有限公司 | Formula and preparation method of high-fluidity degradable polyurethane shoe material |
| CN106565931A (en) * | 2016-08-03 | 2017-04-19 | 广州艾科新材料股份有限公司 | Formula and preparation method for degradable slow-rebound shoe material |
-
2017
- 2017-11-20 CN CN201711159905.3A patent/CN108003323B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1112941A (en) * | 1995-03-24 | 1995-12-06 | 埃勒夫阿托化学有限公司 | Polyaminoester elastic body composition with good buffering characterastic main composition of which are polydiallyl polyhydric alcohol and castor oil |
| CN1982352A (en) * | 2005-12-15 | 2007-06-20 | 上海凯众聚氨酯有限公司 | Production of MDI-polyurethane microporous elastomer |
| WO2008003567A1 (en) * | 2006-07-04 | 2008-01-10 | Huntsman International Llc | Process for making visco-elastic foams |
| CN102159610A (en) * | 2008-07-18 | 2011-08-17 | 陶氏环球技术有限责任公司 | Natural resource based viscoelastic foams |
| CN101948616A (en) * | 2010-09-13 | 2011-01-19 | 安徽大学 | Microporous polyurethane elastomer shock absorption element for high-speed railway and preparation method thereof |
| CN106632962A (en) * | 2016-11-08 | 2017-05-10 | 佛山林至高分子材料科技有限公司 | Plant oil-based cartilage bionic buffer damping material and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 蓖麻油-聚醚基聚氨酯弹性体的制备和表征;杜辉;《化工新材料》;20090228;第37卷(第2期);第106-108页 * |
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