CN111607062B - Biomass polyurethane foam material and preparation method thereof - Google Patents
Biomass polyurethane foam material and preparation method thereof Download PDFInfo
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- CN111607062B CN111607062B CN202010479196.2A CN202010479196A CN111607062B CN 111607062 B CN111607062 B CN 111607062B CN 202010479196 A CN202010479196 A CN 202010479196A CN 111607062 B CN111607062 B CN 111607062B
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- polyether polyol
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- polyurethane foam
- polyurethane
- biomass
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- 239000000463 material Substances 0.000 title claims abstract description 109
- 239000002028 Biomass Substances 0.000 title claims abstract description 62
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
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- 239000004814 polyurethane Substances 0.000 claims abstract description 67
- 150000003077 polyols Chemical class 0.000 claims abstract description 64
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- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 53
- 229920000570 polyether Polymers 0.000 claims abstract description 53
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 51
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- 239000000843 powder Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 20
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- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 18
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- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 14
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- 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 9
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- 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 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- MSHKXFDHUIFHMD-UHFFFAOYSA-N n-benzyl-n-butylbutan-1-amine Chemical compound CCCCN(CCCC)CC1=CC=CC=C1 MSHKXFDHUIFHMD-UHFFFAOYSA-N 0.000 claims description 2
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 6
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 241000609240 Ambelania acida Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
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- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
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- 239000000853 adhesive Substances 0.000 description 1
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to the field of polyurethane materials, and discloses a biomass polyurethane foam material and a preparation method thereof. Specifically, the method comprises the following steps: under the assistance of polyethylene glycol and acetic acid, the micro-shearing of an internal mixer is utilized to carry out phenol hydroxylation treatment on the surface of the wood fiber, so that the skeleton of the wood fiber is fully reserved; and the inorganic fiber is assisted, so that the wear resistance and strength of the polyurethane are effectively improved. The material A obtained after the modified wood fiber is mixed with polyether polyol is paste. In order to adapt to industrial production and application, isocyanate is subjected to pre-polymerization treatment and is matched with a microporous inorganic adsorption prepolymer, so that the material B is also in a paste shape, and the material A, B is kneaded and mixed in the paste shape for use. Can be directly prepared into shoe soles, automobile bumpers, floors, heat-insulating sheet polyurethane foam materials and the like according to the selection of a mould. The prepared biomass polyurethane foam material has good mechanical property, good degradation property after use, and no pollution to the environment after use.
Description
Technical Field
The invention relates to the field of polyurethane materials, in particular to a biomass polyurethane foam material and a preparation method thereof.
Background
Polyurethane is a polymer containing many urethane segments that can be synthesized by a variety of chemical methods, the most common being the reaction of a polyisocyanate with an organic polyol (polyol). By changing the type and composition of the raw materials, the product form and properties can be changed, and a soft to hard final product can be obtained. For example, polyurethane products are in the forms of flexible, semi-rigid and rigid foams, elastomers, paint coatings, adhesives, sealants, synthetic leather coating resins, elastic fibers and the like. Because of the numerous forms and characteristics of polyurethane, polyurethane gradually becomes a polymer material which is widely applied at present.
Compared with the complex polymerization reaction of other common high polymer materials, the polymerization of polyurethane is much simpler. The polymerization of polyurethanes is primarily a direct reaction from the typical liquid monomers. For example, most of the precursor monomers of polyurethane used in industrial production are in liquid state, and the processing mode is to mix two-component liquid to initiate polymerization reaction, so that the application of the polyurethane is more diversified, and various components are prepared by directly pouring or molding the precursor components. More excellent, the polyisocyanate component is easy to react quickly, but the polyol component is stable, and a catalyst, a surfactant, a flame retardant, a filler and the like can be added in advance and dispersed uniformly, so that the storage and the use of the two components are more convenient.
Because of the advantages of the polyurethane such as abrasion resistance, tear resistance, bending resistance and the like. The dosage of the traditional Chinese medicine composition in the fields of furniture, clothes, shoe materials, household appliances, automobiles and the like is increased sharply at present. Most of raw materials for producing polyurethane come from non-renewable resources such as petroleum, coal and the like, so that the supply cost of the raw materials is increased year by year. In particular, since the application field of polyurethane is wide, unlike general polymer plastics, it is difficult to recover it. Such as shoe materials, cushioning packaging, heat insulating materials, etc., are difficult to recycle. The polyurethane material is difficult to degrade and the waste thereof is difficult to recover, thereby facing the problem of environmental pollution.
In order to realize the continuous development and the green and environment-friendly development of polyurethane, the development of biomass polyurethane by using biomass materials becomes a better way for solving the problems of raw material shortage and environmental pollution. The initial biomass polyurethane was prepared by filling a biomass material in polyurethane, and the biomass material was used only as a simple filler, but the problem of the raw material could not be solved although the polyurethane was given a certain biodegradability, and the mechanical properties of the polyurethane were greatly affected by direct filling. In recent years, polyols for preparing polyurethane by using biomass products instead of petroleum raw materials are developed, and great breakthroughs are made in solving the problems of polyol raw materials and degradability. The main raw materials of the polyurethane are polyester polyol and polyether polyol, and most of plant raw materials are not only natural compounds rich in hydroxyl, but also have stable three-dimensional network structures, so that the polyurethane has the great advantage of replacing petroleum polyol. The waste straw, stalk, bagasse and other plant material contain great amount of cellulose, hemicellulose, lignin and other polyhydroxy compounds. The polyester polyol and the polyether polyol can be obtained by a liquefaction modification method and become better polyurethane raw materials. For example, biological raw materials such as wood, rice straw, straw and the like are liquefied by using a polyethylene glycol liquefying agent under the catalysis of acid, the obtained polyol reacts with organic polyisocyanate to synthesize polyurethane, and the polyurethane has better degradation performance because natural polysaccharide components capable of being naturally degraded are introduced into a polyurethane chain segment.
Chinese invention patent CN201110034192.4 discloses a method for preparing polyurethane foam material by using biomass waste and papermaking black liquor extract as main raw materials, which adopts cheap and easily available biomass waste as raw material, and uses the liquefied product of the biomass waste to completely replace polymeric polyol, thereby fully utilizing the waste generated in agricultural production; in addition, lignosulfonate is extracted from the papermaking black liquor and added into the biomass degradation liquid, a method for properly treating the papermaking black liquor is found while the raw material cost is reduced, the prepared polyurethane foam material has good degradation performance due to the addition of biomass components, the environment is not polluted after the polyurethane foam material is used, wastes in agricultural production and papermaking industries are effectively utilized, the raw material cost is greatly reduced, and a new value-added way is found for the wastes generated in the agricultural production and papermaking industries.
At present, the technology for obtaining plant fiber polyether polyol by using plant fibers at home and abroad mainly comprises 5 types, namely a high-temperature liquefaction modification technology, a medium-low temperature liquefaction technology, a selective process liquefaction technology, a biological enzymolysis technology, a separation direct application technology and the like. The energy consumption of the direct separation application technology is high, and the technology is subject to elimination; the biological enzymolysis technology has low energy efficiency and is still in an experimental stage; the production safety of the high-temperature liquefaction modification technology and the selective process liquefaction technology is slightly poor; the medium-low temperature liquefaction technology is synthesized under the conditions of normal temperature and normal pressure, has high production safety, good product stability and high yield, and is the mainstream technology for synthesizing the plant fiber polyether polyol in China. However, there are also technical barriers to the use of biomass material polyols in polyurethanes compared to the polyol structure of petroleum-based polyols. On one hand, the complete liquefaction and polyatomic alcohol treatment process of the biomass material is complex, a large amount of auxiliary agents are consumed, and the liquefaction yield is low, the impurities are more, and the color is dark; on the other hand, polyether polyol obtained by liquefying a biomass material has poor physical and chemical properties, and currently, research and development of bio-based polyurethane mainly uses biomass-based polyether to replace petroleum-based polyether, so that the bio-based polyether is required to have physical and chemical properties similar to those of petroleum-based polyether, but the physical and chemical properties are difficult to achieve. More importantly, the wear resistance, elasticity and mechanical properties of polyurethane prepared by using the biomass treated polyol are different from those of petroleum-based polyurethane, and the use of the polyurethane is influenced.
Disclosure of Invention
According to the above, in the development of biomass polyurethane, complete liquefaction and polyalcohol of biomass is used as a raw material of polyurethane, which causes a problem of high liquefaction cost; meanwhile, although the biomass polyol promotes the biomass degradation of the polyurethane, the physical and chemical properties of the polyurethane are poor, and particularly the wear resistance, elasticity and mechanical properties are greatly reduced. The developed biomass polyurethane is hopeful to be used for shoe materials, and has higher requirements on wear resistance, elasticity and mechanical properties. Obviously, whether the biomass is directly used as a filling material for polyurethane or the biomass is liquefied into polyol to prepare polyurethane, the obtained polyurethane is not suitable as a shoe material.
In view of the above, the present invention provides a biomass polyurethane foam material different from the prior art, which is characterized in that wood fiber is subjected to phenol hydroxylation on the surface of the wood fiber through a simple banburying process, and the wood fiber and polyether polyol are prepared into a paste; further, the isocyanate is changed into paste by utilizing the adsorption of a porous inorganic substance; and (3) extruding the two-component paste to perform reaction foaming to obtain the biomass polyurethane foaming material.
In order to achieve the above object, firstly, a preparation method of a biomass polyurethane foam material is provided, which is characterized by comprising the following steps:
s1: uniformly mixing wood fiber, polyethylene glycol and acetic acid, then adding into an internal mixer for internal mixing at 80-90 ℃ for 20-30min, further adding high-resilience polyether polyol and inorganic fiber for internal mixing uniformly, and discharging;
s2, adding a chain extender, a catalyst, a foam stabilizer and water into the material obtained in the step S1, and stirring the mixture into a uniform paste material A;
s3: dehydrating polyether polyol at 100 ℃ in vacuum until the water content is less than 0.05%, then cooling to 50 ℃, uniformly stirring and mixing the polyether polyol with isocyanate, porous inorganic powder and spherical inorganic powder, gradually heating to 70-80 ℃, and carrying out low-speed stirring and prepolymerization for 25-35min to obtain a prepolymerized paste material B;
s4: utilizing a spiral feeder to mix the material A and the material B according to the mass ratio of 1: feeding the biomass polyurethane foaming material at room temperature by two spiral feeders according to the proportion of 1-1.2, quickly kneading and uniformly mixing in a kneading machine, injecting into a mold, and foaming and curing at 50-55 ℃ for 5-7min to obtain the biomass polyurethane foaming material.
Preferably, the wood fiber, the polyethylene glycol, the acetic acid, the high resilience polyether polyol and the inorganic fiber in the step S1 are calculated according to the parts by weight, wherein the wood fiber accounts for 20-25 parts by weight, the polyethylene glycol accounts for 3-5 parts by weight, the acetic acid accounts for 0.5-1.0 part by weight, the high resilience polyether polyol accounts for 100-120 parts by weight and the inorganic fiber accounts for 3-5 parts by weight. Different from the prior method that the wood fiber is liquefied for a long time by using excessive polyethylene glycol, the method utilizes less polyethylene glycol and acetic acid, utilizes the mixing of an internal mixer to modify the wood fiber, maintains the fiber structure of the wood fiber, simultaneously increases the content of phenolic hydroxyl on the surface of the wood fiber under the actions of polyethylene glycol, acetic acid and micro-shearing of the internal mixer, is easy to form uniform dispersion on polyether glycol, and is easy to polymerize with isocyanate.
Further preferably, the high resilience polyether polyol in step S1 is EP330N polyether polyol, and the hydroxyl value is 33-37 mgKOH/g.
Further preferably, in step S1, the inorganic fiber is at least one of a glass fiber, a wollastonite fiber, a ceramic fiber, a calcium carbonate whisker and a calcium sulfate whisker; used for assisting in increasing the abrasion resistance and strength of the polyurethane.
Preferably, in the step S2, the chain extender is a chain extender commonly used in the field of polyurethane, specifically, at least one of 1, 4-butanediol, ethylene glycol and propylene glycol is selected; the addition amount of the chain extender is 2-3% of the mass of the high resilience polyether polyol.
Preferably, the catalyst in step S2 is selected from an organic amine compound or/and an organic tin compound; further preferably, the organic amine compound is selected from triethylene diamine and benzyl dibutyl amine; the organic tin compound is dibutyltin dilaurate, tin 2-ethyl hexanoate, stannous octoate and tin octoate; the typical application is that a compound of dibutyltin dilaurate and triethylene diamine in a mass ratio of 2:1 is selected as a catalyst; the adding amount is 0.5-1% of the mass of the high resilience polyether polyol.
Preferably, dimethyl siloxane is selected as the foam stabilizer in the step S2, and the adding amount is 1-1.5% of the mass of the polyether polyol.
Preferably, the amount of water added in step S2 is 0.1-0.5% by mass of the polyether polyol.
Preferably, the polyether polyol, the isocyanate, the porous inorganic powder and the spherical inorganic powder are mixed in step S3 according to the parts by weight, wherein the polyether polyol is 80-90 parts by weight, the isocyanate is 120-130 parts by weight, the porous inorganic powder is 10-15 parts by weight, and the spherical inorganic powder is 3-5 parts by weight.
Further preferably, in step S3, the polyether polyol is DL3000D, the hydroxyl value is 35-39mg KOH/g, and the acid value is less than or equal to 0.05mg KOH/g.
Further preferably, in step S3, 4-diphenylmethane diisocyanate is used as the isocyanate; the porous inorganic substance powder is at least one of fumed silica with a porosity of more than 50%, zeolite powder with a porosity of more than 65% and microporous glass powder with a porosity of more than 40%; particularly, the particle size of the porous inorganic powder is 20-50 microns; the porous inorganic powder can absorb part of the prepolymer so as to change from liquid to paste; the spherical inorganic substance powder is one of barium sulfate and glass microspheres with the sphericity of more than 80%. The higher sphericity makes the paste easy to slip and disperse. In addition, the wear resistance of the polyurethane is further enhanced by adding the porous inorganic powder and the inorganic powder.
Preferably, the mold in step S4 is selected according to the product requirements of polyurethane. For example, in order to obtain a sheet-like polyurethane foam, a sheet mold is provided; in order to obtain, for example, a sole, the mould is provided as a sole mould.
The invention also provides a biomass polyurethane foam material prepared by the method. The incomplete liquefaction of the wood fibers to obtain polyols, although capable of producing biomass polyurethanes, nevertheless suffers from poor mechanical properties of the polyurethanes, which in turn affects the use thereof. Therefore, the surface of the wood fiber is subjected to phenol hydroxylation treatment by utilizing micro-shearing of an internal mixer under the assistance of polyethylene glycol and acetic acid, so that the wood fiber is easy to uniformly disperse in polyether polyol and is easy to react with isocyanate, the skeleton of the wood fiber is fully reserved, and the polyurethane retains better mechanical property while the biodegradability is endowed to the polyurethane; furthermore, the wear resistance and strength of the polyurethane are effectively improved by the aid of inorganic fibers. In particular, since the wood fiber used is a surface-modified wood fiber, not a completely liquefied wood fiber, the material a obtained after mixing the modified wood fiber with the polyether polyol is a paste. In order to adapt to industrial production and application, the invention carries out prepolymerization treatment on isocyanate and is matched with an inorganic substance adsorption prepolymer with micropores, so that the material B is also in a paste shape, and the material A, B is kneaded and mixed to be used in the form of the paste.
Compared with the prior art, the invention has the following excellent effects:
1. compared with the prior art that the wood fiber is directly dispersed in the polyurethane, the invention ensures that the binding property and the compatibility of the wood fiber in the polyurethane are better through the phenol hydroxylation treatment on the surface of the wood fiber.
2. Compared with the prior art that the mechanical property is influenced by completely liquefying wood fiber into polyol to prepare polyurethane, the invention reserves the fiber structure of the wood fiber, so that the mechanical property is reserved, and meanwhile, the wood fiber subjected to phenol hydroxylation is easy to react with isocyanate to form a whole, so that the wood fiber is not only a framework, but also an auxiliary reactant, and the biomass property of the polyurethane is endowed.
3. The invention is based on the technical barrier of the prior biomass material for polyurethane, in order to realize large-scale preparation and use of the biomass polyurethane, the wood fiber is processed by a simple and easy method, and the paste-shaped double components are processed and used in molding, and can be directly prepared into soles, automobile bumpers, floors, heat-insulating sheets and the like according to the selection of a mold. The prepared biomass polyurethane foam material has good mechanical property, good degradation property after use, and no pollution to the environment after use.
Drawings
The invention is further described below with reference to the accompanying drawings:
FIG. 1 is a flow chart of a preparation process of a biomass polyurethane foam material of the invention.
Detailed Description
The present invention is further illustrated by the following examples, which are presently preferred and illustrative, but are not intended to limit the scope of the invention. In addition, the adopted comparative examples are mainly used for carrying out qualitative relative comparison, and in order to ensure accurate comparison of experiments, the raw materials selected by the comparative examples are all the raw materials consistent with the examples.
Example 1
S1: 20kg of wood fiber provided by Yixing Shangpo building materials Co., Ltd, 4kg of polyethylene glycol 400 and 0.5kg of acetic acid are mixed uniformly, and then the mixture is put into an internal mixer to be mixed for 30min at the temperature of 80 ℃, wherein the mixing rotating speed is 30 rpm; further adding 100kg of EP330N polyether polyol and 3kg of glass fiber, continuously banburying for 5min till the mixture is uniform, and discharging;
s2, adding a chain extender, a catalyst, a foam stabilizer and water into the material obtained in the step S1, and stirring the mixture into a uniform paste material A; the chain extender is 1, 4-butanediol, and the adding amount is 2% of the weight of EP 330N; the catalyst is a compound of dibutyltin dilaurate and triethylene diamine according to the mass ratio of 2:1, and the adding amount of the compound is 0.5% of the mass of EP 330N; dimethyl siloxane is selected as the foam stabilizer, and the adding amount is 1 percent of the mass of EP 330N; the amount of water added was 0.3% by mass of EP 330N.
S3: vacuum dehydrating 80kg of polyether polyol DL3000D at 100 ℃ until the water content is less than 0.05 percent, then cooling to 50 ℃, adding 120kg of 4, 4-diphenylmethane diisocyanate, further adding 10kg of fumed silica with the granularity of 20-50 microns and the porosity of more than 50 percent, adding 3kg of barium sulfate with the sphericity of more than 80 percent, gradually heating to 70 ℃, and carrying out low-speed stirring and prepolymerization for 25min to obtain a prepolymerization paste material B;
s4: utilizing a spiral feeder to mix the material A and the material B according to the mass ratio of 1: feeding the biomass polyurethane foam material at room temperature by two spiral feeders according to the proportion of 1, quickly kneading and uniformly mixing in a kneading machine, injecting into a sheet die, and foaming and curing at 50 ℃ for 7min to obtain the biomass polyurethane foam material.
Example 2
S1: uniformly mixing 22kg of wood fiber, 5kg of polyethylene glycol 400 and 1kg of acetic acid provided by Yixing City Vigorboom building materials Co., Ltd, and then putting into an internal mixer to carry out internal mixing for 30min at 90 ℃, wherein the internal mixing rotating speed is 30 rpm; further adding 110kg of EP330N polyether polyol and 3kg of ceramic fiber, continuously banburying for 10min until the mixture is uniform, and discharging;
s2, adding a chain extender, a catalyst, a foam stabilizer and water into the material obtained in the step S1, and stirring the mixture into a uniform paste material A; ethylene glycol is selected as the chain extender, and the adding amount is 3 percent of the mass of EP 330N; the catalyst is a compound of dibutyltin dilaurate and triethylene diamine according to the mass ratio of 2:1, and the adding amount of the compound is 0.5% of the mass of EP 330N; dimethyl siloxane is selected as the foam stabilizer, and the adding amount is 1 percent of the mass of EP 330N; the amount of water added was 0.4% by mass of EP 330N.
S3: vacuum dehydrating 90kg of polyether polyol DL3000D at 100 ℃ until the water content is less than 0.05 percent, then cooling to 50 ℃, adding 120kg of 4, 4-diphenylmethane diisocyanate, further adding 10kg of microporous glass powder with the granularity of 20-50 microns and the porosity of more than 40 percent, adding 3kg of barium sulfate with the sphericity of more than 80 percent, gradually heating to 80 ℃, and carrying out low-speed stirring and prepolymerization for 35min to obtain a prepolymerization paste material B;
s4: utilizing a spiral feeder to mix the material A and the material B according to the mass ratio of 1: feeding the biomass polyurethane foam material at room temperature by two spiral feeders according to the proportion of 1.2, quickly kneading and uniformly mixing in a kneading machine, injecting into a mold, foaming and curing at 55 ℃ for 5min to obtain the biomass polyurethane foam material.
Example 3
S1: uniformly mixing 25kg of wood fiber, 5kg of polyethylene glycol 400 and 0.8kg of acetic acid provided by Yixing Shangpo building materials Co., Ltd, and then putting the mixture into an internal mixer to mix for 30min at 90 ℃, wherein the mixing speed is 30 rpm; further adding 100kg of EP330N polyether polyol and 5kg of glass fiber, continuously banburying for 15min until the mixture is uniform, and discharging;
s2, adding a chain extender, a catalyst, a foam stabilizer and water into the material obtained in the step S1, and stirring the mixture into a uniform paste material A; the chain extender is 1, 4-butanediol, and the adding amount is 3% of the weight of EP 330N; the catalyst is a compound of dibutyltin dilaurate and triethylene diamine according to a mass ratio of 2:1, and the adding amount of the compound is 1% of the mass of EP 330N; dimethyl siloxane is selected as the foam stabilizer, and the adding amount is 1.5 percent of the weight of EP 330N; the amount of water added was 0.3% by mass of EP 330N.
S3: dehydrating 85kg of polyether polyol DL3000D at 100 ℃ in vacuum until the water content is less than 0.05 percent, then cooling to 50 ℃, adding 130kg of 4, 4-diphenylmethane diisocyanate, further adding 15kg of fumed silica with the granularity of 20-50 microns and the porosity of more than 50 percent, adding 4kg of glass microspheres with the sphericity of more than 80 percent, gradually heating to 70 ℃, and carrying out low-speed stirring and prepolymerization for 30min to obtain a prepolymerization paste material B;
s4: utilizing a spiral feeder to mix the material A and the material B according to the mass ratio of 1: feeding the biomass polyurethane foam material at room temperature by two spiral feeders according to the proportion of 1, quickly kneading and uniformly mixing in a kneading machine, injecting into a mold, foaming and curing at 55 ℃ for 7min to obtain the biomass polyurethane foam material.
Comparative example 1
S1: uniformly mixing 20kg of wood fiber, 40kg of polyethylene glycol 400 and 2.5kg of acetic acid provided by Yixing Shangpo building materials Co., Ltd, and then putting the mixture into an internal mixer to mix for 60min at 80 ℃, wherein the mixing speed is 30rpm, and the material is thinned; further adding 100kg of EP330N polyether polyol and 3kg of glass fiber, continuously banburying for 5min till the mixture is uniform, and discharging;
s2, adding a chain extender, a catalyst, a foam stabilizer and water into the material obtained in the step S1, and stirring the mixture into a uniform alkene-shaped material A; the chain extender is 1, 4-butanediol, and the adding amount is 2% of the weight of EP 330N; the catalyst is a compound of dibutyltin dilaurate and triethylene diamine according to the mass ratio of 2:1, and the adding amount of the compound is 0.5% of the mass of EP 330N; dimethyl siloxane is selected as the foam stabilizer, and the adding amount is 1 percent of the mass of EP 330N; the amount of water added was 0.3% by mass of EP 330N.
S3: vacuum dehydrating 80kg of polyether polyol DL3000D at 100 ℃ until the water content is less than 0.05 percent, then cooling to 50 ℃, adding 120kg of 4, 4-diphenylmethane diisocyanate, further adding 10kg of fumed silica with the granularity of 20-50 microns and the porosity of more than 50 percent, adding 3kg of barium sulfate with the sphericity of more than 80 percent, gradually heating to 70 ℃, and carrying out low-speed stirring and prepolymerization for 25min to obtain a prepolymerization paste material B;
s4: utilizing a spiral feeder to mix the material A and the material B according to the mass ratio of 1: feeding the biomass polyurethane foam material at room temperature by two spiral feeders according to the proportion of 1, quickly kneading and uniformly mixing in a kneading machine, injecting into a sheet die, and foaming and curing at 50 ℃ for 7min to obtain the biomass polyurethane foam material.
Comparative example 1 added more polyethylene glycol and acetic acid, and lengthened the banburying shearing time, made the plant fiber liquefaction degree deepen. The structural damage of the vegetable fibres is severe, affecting the strength and wear resistance of the final polyurethane.
Comparative example 2
S1: 20kg of wood fiber provided by Yixing Shangpo building materials Co., Ltd, 4kg of polyethylene glycol 400 and 0.5kg of acetic acid are mixed uniformly, and then the mixture is put into an internal mixer to be mixed for 30min at the temperature of 80 ℃, wherein the mixing rotating speed is 30 rpm; further adding 100kg of EP330N polyether polyol, continuously banburying for 5min till uniformity, and discharging;
s2, adding a chain extender, a catalyst, a foam stabilizer and water into the material obtained in the step S1, and stirring the mixture into a uniform paste material A; the chain extender is 1, 4-butanediol, and the adding amount is 2% of the weight of EP 330N; the catalyst is a compound of dibutyltin dilaurate and triethylene diamine according to the mass ratio of 2:1, and the adding amount of the compound is 0.5% of the mass of EP 330N; dimethyl siloxane is selected as the foam stabilizer, and the adding amount is 1 percent of the mass of EP 330N; the amount of water added was 0.3% by mass of EP 330N.
S3: vacuum dehydrating 80kg of polyether polyol DL3000D at 100 ℃ until the water content is less than 0.05 percent, then cooling to 50 ℃, adding 120kg of 4, 4-diphenylmethane diisocyanate, further adding 10kg of fumed silica with the granularity of 20-50 microns and the porosity of more than 50 percent, adding 3kg of barium sulfate with the sphericity of more than 80 percent, gradually heating to 70 ℃, and carrying out low-speed stirring and prepolymerization for 25min to obtain a prepolymerization paste material B;
s4: utilizing a spiral feeder to mix the material A and the material B according to the mass ratio of 1: feeding the biomass polyurethane foam material at room temperature by two spiral feeders according to the proportion of 1, quickly kneading and uniformly mixing in a kneading machine, injecting into a sheet die, and foaming and curing at 50 ℃ for 7min to obtain the biomass polyurethane foam material.
Comparative example 2 no glass fibers were added to the a-pack, which had an effect on the strength and abrasion resistance of the final polyurethane.
Comparative example 3
S1: 20kg of wood fiber provided by Yixing Shangpo building materials Co., Ltd, 4kg of polyethylene glycol 400 and 0.5kg of acetic acid are mixed uniformly, and then the mixture is put into an internal mixer to be mixed for 30min at the temperature of 80 ℃, wherein the mixing rotating speed is 30 rpm; further adding 100kg of EP330N polyether polyol and 3kg of glass fiber, continuously banburying for 5min till the mixture is uniform, and discharging;
s2, adding a chain extender, a catalyst, a foam stabilizer and water into the material obtained in the step S1, and stirring the mixture into a uniform paste material A; the chain extender is 1, 4-butanediol, and the adding amount is 2% of the weight of EP 330N; the catalyst is a compound of dibutyltin dilaurate and triethylene diamine according to the mass ratio of 2:1, and the adding amount of the compound is 0.5% of the mass of EP 330N; dimethyl siloxane is selected as the foam stabilizer, and the adding amount is 1 percent of the mass of EP 330N; the amount of water added was 0.3% by mass of EP 330N.
S3: vacuum dehydrating 80kg of polyether polyol DL3000D at 100 ℃ until the water content is less than 0.05 percent, then cooling to 50 ℃, adding 120kg of 4, 4-diphenylmethane diisocyanate, further adding 10kg of fumed silica with the granularity of 20-50 microns and the porosity of more than 50 percent, gradually heating to 70 ℃, stirring at low speed and carrying out prepolymerization for 25min to obtain a prepolymerized paste material B;
s4: utilizing a spiral feeder to mix the material A and the material B according to the mass ratio of 1: feeding the biomass polyurethane foam material at room temperature by two spiral feeders according to the proportion of 1, quickly kneading and uniformly mixing in a kneading machine, injecting into a sheet die, and foaming and curing at 50 ℃ for 7min to obtain the biomass polyurethane foam material.
Comparative example 3 the absence of added spherical barium sulphate in the B-side material affects on the one hand the slip properties of the B-side material and thus the homogeneity of the A-and B-side materials and also the abrasion resistance of the polyurethane.
And (3) testing items:
for qualitative comparative analysis, in the case of A, B-material two-component foaming polymerization, the step S4 of examples 1 to 3 and comparative examples 1 to 3 was molded using a sheet mold, and the sheet-shaped biomass polyurethane foam was obtained for performance test.
1. Testing the molding density:
the density was measured by test method A with reference to GB/T533-.
2. And (3) testing tensile strength:
with reference to GB/T6344-2008 "determination of tensile Strength and elongation at Break of Flexible foamed Polymer Material", at least 5 dumbbell-shaped test pieces were cut out with a prototype at a tensile rate of 500. + -.50 mm/mm, and the tensile strength and elongation tested are shown in Table 1.
3. NBS abrasion resistance:
according to ASTM-D1630-2006 Standard test method for rubber wear resistance, a shoe material test piece of 25.4 multiplied by 25.4mm is pre-ground in a testing machine, a certain load is added after the test piece is ground into the area of a friction device, the number of friction wheel turns required for the test piece to reach a certain wear depth is observed, and then the wear resistance is evaluated. And calculating the relative volume abrasion loss of the sole test piece according to the specific gravity of the shoe material test piece and the correction coefficient of the standard rubber, and evaluating the wear resistance of the sole by using the relative volume loss of the sole test piece. The key parameters of the test are as follows: diameter of the rotating wheel: diameter 150mm (outer diameter); loading: 2265g three groups; rotating shaft speed: 45 plus or minus 5 rpm; abrasive paper granularity of 40 #. The test results are shown in table 1.
Table 1:
through the tests, the method adopts the interfacial phenol hydroxylation of the wood fiber and assists the inorganic fiber and the spherical inorganic powder, so that the obtained polyurethane foam material keeps excellent strength and wear resistance. Comparative example 1 added more polyethylene glycol and acetic acid and lengthened banburying shearing and made the plant fiber liquefaction degree deepen, the structure of plant fiber destroys seriously, thus influence final polyurethane intensity and wearability. Comparative example 2 no glass fibers were added to the a-pack, which had an effect on the strength and abrasion resistance of the final polyurethane. Comparative example 3 the absence of added spherical barium sulphate to the B material affects the abrasion resistance of the polyurethane.
It is to be understood that the exemplary embodiments described herein are to be considered as illustrative and not restrictive. Moreover, descriptions of features or aspects in various embodiments should be applicable to other similar features or aspects in other embodiments.
While one or more embodiments of the present invention have been illustrated in the accompanying drawings, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims.
Claims (7)
1. A preparation method of a biomass polyurethane foam material is characterized by comprising the following steps:
s1: uniformly mixing wood fiber, polyethylene glycol and acetic acid, then adding into an internal mixer for internal mixing at 80-90 ℃ for 20-30min, further adding high-resilience polyether polyol and inorganic fiber for internal mixing uniformly, and discharging; wherein, the wood fiber accounts for 20 to 25 weight portions, the polyethylene glycol accounts for 3 to 5 weight portions, the acetic acid accounts for 0.5 to 1.0 weight portion, the high resilience polyether polyol accounts for 100 to 120 weight portions, and the inorganic fiber accounts for 3 to 5 weight portions; the high resilience polyether polyol is EP330N polyether polyol, and the hydroxyl value is 33-37 mgKOH/g; the inorganic fiber is at least one of glass fiber, wollastonite fiber, ceramic fiber, calcium carbonate whisker and calcium sulfate whisker;
s2, adding a chain extender, a catalyst, a foam stabilizer and water into the material obtained in the step S1, and stirring the mixture into a uniform paste material A;
s3: dehydrating polyether polyol at 100 ℃ in vacuum until the water content is less than 0.05%, then cooling to 50 ℃, uniformly stirring and mixing the polyether polyol with isocyanate, porous inorganic powder and spherical inorganic powder, gradually heating to 70-80 ℃, and carrying out low-speed stirring and prepolymerization for 25-35min to obtain a prepolymerized paste material B;
s4: utilizing a spiral feeder to mix the material A and the material B according to the mass ratio of 1: feeding the biomass polyurethane foaming material at room temperature by two spiral feeders according to the proportion of 1-1.2, quickly kneading and uniformly mixing in a kneading machine, injecting into a mold, and foaming and curing at 50-55 ℃ for 5-7min to obtain the biomass polyurethane foaming material.
2. The preparation method of the biomass polyurethane foam material as claimed in claim 1, wherein the preparation method comprises the following steps: in the step S2, at least one of 1, 4-butanediol, ethylene glycol and propylene glycol is selected as the chain extender, and the addition amount of the chain extender is 2-3% of the mass of the high resilience polyether polyol; the catalyst is selected from organic amine compounds or/and organic tin compounds, and the adding amount of the organic amine compounds or/and organic tin compounds is 0.5-1% of the mass of the high-resilience polyether polyol; the foam stabilizer is dimethyl siloxane, and the adding amount of the foam stabilizer is 1-1.5% of the mass of polyether polyol; the addition amount of the water is 0.1-0.5% of the mass of the polyether polyol.
3. The preparation method of the biomass polyurethane foam material as claimed in claim 2, wherein the preparation method comprises the following steps: the organic amine compound is one of triethylene diamine and benzyl dibutyl amine; the organic tin compound is one of dibutyltin dilaurate, tin 2-ethyl hexanoate, stannous octoate and tin octoate.
4. The preparation method of the biomass polyurethane foam material as claimed in claim 1, wherein the preparation method comprises the following steps: in the step S3, the polyether polyol, the isocyanate, the porous inorganic powder and the spherical inorganic powder are mixed according to the parts by weight, wherein the parts by weight of the polyether polyol is 80-90, the parts by weight of the isocyanate is 120-130, the parts by weight of the porous inorganic powder is 10-15 and the parts by weight of the spherical inorganic powder is 3-5.
5. The preparation method of the biomass polyurethane foam material as claimed in claim 1, wherein the preparation method comprises the following steps: the polyether polyol is selected from DL3000D, the hydroxyl value is 35-39mg KOH/g, and the acid value is less than or equal to 0.05mg KOH/g; the isocyanate is 4, 4-diphenylmethane diisocyanate.
6. The preparation method of the biomass polyurethane foam material as claimed in claim 1, wherein the preparation method comprises the following steps: the porous inorganic substance powder is at least one of fumed silica with a porosity of more than 50%, zeolite powder with a porosity of more than 65% and microporous glass powder with a porosity of more than 40%; the spherical inorganic substance powder is one of barium sulfate and glass microspheres with the sphericity of more than 80%.
7. A biomass polyurethane foam material, characterized by being prepared by the method of any one of claims 1 to 6.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101255112A (en) * | 2008-04-02 | 2008-09-03 | 中国林业科学研究院木材工业研究所 | A method for reusing cellulose-containing materials |
| CN103626948A (en) * | 2013-11-26 | 2014-03-12 | 北京联合大学生物化学工程学院 | Polyurethane foam material synthesized from plant polyols |
| CN104479101A (en) * | 2014-12-31 | 2015-04-01 | 海南大学 | Method for directly preparing polyurethane foam by adopting rice straw as raw material and prepared polyurethane foam |
| CN105175682A (en) * | 2015-09-25 | 2015-12-23 | 南京工业大学 | Process for preparing polyurethane foam by using novel lignin liquefaction method |
| CN111111730A (en) * | 2019-12-19 | 2020-05-08 | 浙江师范大学 | A kind of molybdenum carbide catalyst and its preparation method and application |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1176643A (en) * | 1995-12-29 | 1998-03-18 | K·R·库泼 | Lignin-based polyols |
| JP4651786B2 (en) * | 2000-07-21 | 2011-03-16 | フジカーボン株式会社 | Biomass-derived polyol and biodegradable polyurethane |
| JP2005281374A (en) * | 2004-03-29 | 2005-10-13 | Fuji Carbon Kk | Lignocellulose-derived polyol and method for producing the same, and polyurethane foam |
| CN1974627A (en) * | 2006-12-28 | 2007-06-06 | 李剑飞 | Polyurethane material and its prepn |
| CN102585142B (en) * | 2011-01-14 | 2013-09-04 | 中国林业科学研究院木材工业研究所 | Biomass polyurethane foam and method for preparing same |
| CN102585248B (en) * | 2011-01-14 | 2013-12-04 | 中国林业科学研究院木材工业研究所 | Modified lignin, and preparation method and application thereof |
| CN102174164B (en) * | 2011-01-31 | 2013-01-09 | 中国农业大学 | Method for synthesizing biomass-based polyurethane foam material by using papermaking waste liquor extract |
| CN102206320B (en) * | 2011-04-22 | 2013-04-10 | 中国农业大学 | Preparation method of biomass-base polyurethane foam material |
| CN103992497B (en) * | 2014-04-22 | 2016-07-13 | 南京林业大学 | Method for preparing biomass-based foam material by utilizing natural fiber biomass material |
| CN108060737B (en) * | 2017-08-29 | 2020-08-11 | 北京禾木之家科技发展有限公司 | Preparation method of biomass-based combined wall |
| CN111171264A (en) * | 2018-11-12 | 2020-05-19 | 天津市嘉美特自行车有限公司 | Preparation method of lignin polyurethane |
-
2020
- 2020-05-29 CN CN202010479196.2A patent/CN111607062B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101255112A (en) * | 2008-04-02 | 2008-09-03 | 中国林业科学研究院木材工业研究所 | A method for reusing cellulose-containing materials |
| CN103626948A (en) * | 2013-11-26 | 2014-03-12 | 北京联合大学生物化学工程学院 | Polyurethane foam material synthesized from plant polyols |
| CN104479101A (en) * | 2014-12-31 | 2015-04-01 | 海南大学 | Method for directly preparing polyurethane foam by adopting rice straw as raw material and prepared polyurethane foam |
| CN105175682A (en) * | 2015-09-25 | 2015-12-23 | 南京工业大学 | Process for preparing polyurethane foam by using novel lignin liquefaction method |
| CN111111730A (en) * | 2019-12-19 | 2020-05-08 | 浙江师范大学 | A kind of molybdenum carbide catalyst and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| 竹废料液化制备多羟基化合物研究;刘玉环等;《现代化工》;20081030(第S21期);第224-227页 * |
| 酶解玉米秸秆残渣制备聚氨酯硬质泡沫;张通等;《精细化工》;20180913(第09期);第56-60页 * |
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