WO2021180208A1 - 一种生物质重组的型材及型材的制备方法 - Google Patents

一种生物质重组的型材及型材的制备方法 Download PDF

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WO2021180208A1
WO2021180208A1 PCT/CN2021/080480 CN2021080480W WO2021180208A1 WO 2021180208 A1 WO2021180208 A1 WO 2021180208A1 CN 2021080480 W CN2021080480 W CN 2021080480W WO 2021180208 A1 WO2021180208 A1 WO 2021180208A1
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Prior art keywords
profile
viscous polymer
paper
lignin
acid
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PCT/CN2021/080480
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English (en)
French (fr)
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WO2021180208A9 (zh
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尹应武
任毅华
赵升云
赵玉芬
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厦门大学
武夷学院
北京紫光英力化工技术有限公司
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Priority claimed from CN202010179352.3A external-priority patent/CN113386235B/zh
Priority claimed from CN202010179625.4A external-priority patent/CN112776446A/zh
Priority claimed from CN202010179204.1A external-priority patent/CN113386233B/zh
Application filed by 厦门大学, 武夷学院, 北京紫光英力化工技术有限公司 filed Critical 厦门大学
Publication of WO2021180208A1 publication Critical patent/WO2021180208A1/zh
Publication of WO2021180208A9 publication Critical patent/WO2021180208A9/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse

Definitions

  • the invention relates to the field of bio-based composite materials, and in particular to a biomass-recombined profile and a preparation method of the profile.
  • Biomass new materials are the fundamental direction of human future development, which can best meet the environment, animal/human health, use safety, and meet the requirements of sustainable development.
  • Biomass raw materials are abundant, and wood or bamboo has been used in construction and furniture for thousands of years.
  • bamboo and straw and other biomass have different sizes, poor structure and density uniformity, anisotropy, knotting and growth defects, and their utilization rate has not been high.
  • Papermaking one of the four major inventions in ancient my country, overcomes the above-mentioned problems and achieved a major technological breakthrough in separating plant raw materials into millimeter-level natural color pastes by alkali method, providing a technical and industrial basis for biomass reorganization and molding.
  • the processing method of fiber-plastic composite materials with fiber powder as filler also has problems such as a large decrease in plastic strength, poor product toughness, and a small amount of addition.
  • the hot press molding and blending extrusion molding technology of wood-plastic materials with fiber and plastic as the main components are simple in production process, short cycle, high efficiency, stable product quality, and low production cost
  • the cellulose and semi- Cellulose macromolecules and lignin macromolecules contain a large number of strong polar hydroxyl and ether bonds, which are easy to agglomerate, and are non-polar or weak with thermoplastics such as polyethylene (PE), polypropylene (PP), and polyvinyl chloride (PVC).
  • Polar polymers have poor mixing properties, difficult to disperse, poor fluidity, difficult to process, mechanical properties, especially low toughness, and other technical problems that affect the development of wood-plastic materials need to be solved.
  • Patent document CN1168591C discloses a composite material prepared by a composite of polymer and cellulose fiber.
  • the final composite material contains 30-40% fiber, and the polymer is PP, LDPE, HDPE, PS, and the cellulose fiber is an annual Plant fibers or bast fibers, such as flax, hemp, jute and kenaf, can also be paper fibers, but the prepared fiberboard cannot meet the requirements of ordinary cellulose boards.
  • CN107000383A discloses a multilayer sandwich structure in which a cellulose ester layer is sandwiched between two polymer layers.
  • the cellulose ester can be cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose triacetate, and fiber
  • the sandwich structure can be used to manufacture glass panels with high stiffness and good optical transparency for various applications.
  • the invention is to give full play to the high-strength mechanical properties of the natural color paste separated from bamboo/wood materials, to crack the low strength of man-made fiberboards, difficult to mix wood-plastic materials, low addition of fiber materials, difficult to mix resin and fiber materials uniformly, and high temperature heat.
  • the loss of pressure water affects the strength and other series of problems, solves the problems in the use of series of bio-based composite materials such as low strength of urea-formaldehyde resin, phenolic resin and soybean protein resin, and formaldehyde toxicity.
  • the high-density board of the present invention is compared with the national standard GB/T 31765-2015, and the product sample size, density, moisture content, tensile strength, static flexural strength (flexural strength) and elastic modulus (three-point bending, or called It is flexural modulus), impact toughness, internal bonding strength, 24h water absorption thickness expansion rate performance test all adopt the method described in the national standard GB/17657-2013.
  • the present invention has developed a new type of composite profile, characterized in that the profile contains cellulose and viscous polymer, the static flexural strength of the profile is 40-500MPa, the modulus of elasticity is 4000-40000Mpa, cellulose and The mass ratio of the viscous polymer is 1: (0.01-100).
  • cellulose is a chain polymer of D-glucose combined with ⁇ -1,4 glycosidic bonds.
  • the viscous polymer is a high-molecular polymer with viscosity, and the high-molecular polymer can achieve viscous properties under normal temperature or heating, or has viscous properties when an organic solvent or water is used as a solvent.
  • the static flexural strength of the profile is 45-120 MPa
  • the elastic modulus is 5000-12000 MPa
  • the mass ratio of cellulose and viscous polymer is 1: (0.1-10.0).
  • the static flexural strength of the profile is 50-200MPa, and the elastic modulus is 6000-15000Mpa; or, the mass ratio of cellulose and viscous polymer is 1:(0.1-10.0).
  • the static flexural strength of the profile is 100-500MPa
  • the elastic modulus is 10000-35000Mpa
  • the mass ratio of cellulose and viscous polymer is 1:(0.1-10.0).
  • the static flexural strength of the profile is 45-100MPa
  • the elastic modulus is 5000-12000Mpa
  • the mass ratio of cellulose and viscous polymer is 1:(0.1-5.0).
  • the fiber The mass ratio of the cellulose and the viscous polymer is 1: (0.2-4.0). More preferably, the mass ratio of the cellulose and the viscous polymer is 1: (0.5-3.1).
  • the static flexural strength of the profile is 50-130MPa
  • the elastic modulus is 6000-15000Mpa
  • the mass ratio of cellulose and viscous polymer is 1: (0.1-7.0).
  • the fiber The mass ratio of the cellulose to the viscous polymer is 1: (0.6-5.0), particularly preferably, the mass ratio of the cellulose to the viscous polymer is 1: (0.2-2.0).
  • the static flexural strength of the profile is 100-500 MPa, and the elastic modulus is 10000-35000 Mpa, and preferably, the tensile strength of the profile is 50-300 MPa.
  • the static flexural strength of the profile is 200-400MPa
  • the tensile strength is 110-250MPa
  • the modulus of elasticity is 13000-30000Mpa
  • the mass ratio of cellulose and viscous polymer is 1:(0.1- 5.0), especially preferably, the mass ratio of cellulose and viscous polymer is 1: (0.2-3.0).
  • the thickness of the profile is less than or equal to 3.5 mm.
  • the cellulose and the viscous polymer are evenly distributed. That is, from the perspective of cellulose, the cellulose is uniformly distributed in the viscous polymer; conversely, from the perspective of the viscous polymer, the viscous polymer is uniformly distributed in the cellulose.
  • the above profile is proved by the examples of the present invention, which is characterized by containing cellulose and viscous polymer.
  • the content of cellulose and viscous polymer can be determined according to the addition amount of the raw material. If the raw material is unknown, the product through the profile is also Can be measured. The range is within the above range. The static bending strength and elastic modulus of the profile are within a certain range. From these two indicators, its performance is better than that of high-density fiberboard.
  • the viscous polymer contains acid-insoluble lignin, and the mass percentage of the acid-insoluble lignin in the profile is 1-80%.
  • the viscous polymer contains acid-insoluble lignin, and the acid-insoluble lignin accounts for 1-60% of the mass of the profile.
  • the acid-insoluble lignin accounts for 5 to 60% of the mass of the profile. 55%, especially preferably, the mass percentage of acid-insoluble lignin in the profile is 9.0-53.0%.
  • the acid-insoluble lignin includes the acid-insoluble lignin and exogenous acid-insoluble lignin derived from the raw materials for the preparation of profiles.
  • the lignin derived from the raw materials for the preparation of profiles accounts for 1-28% of the content of the profiles.
  • the percentage of exogenous acid-insoluble lignin in the profile is 1-25%.
  • the viscous polymer contains not only acid-insoluble lignin, but also bio-based calcium sulfonate, polypropylene (PP), polyethylene (PE), polyvinyl chloride (PVC), and polylactic acid.
  • PP polypropylene
  • PE polyethylene
  • PVC polyvinyl chloride
  • PLA polyamide
  • PA polyethylene terephthalate
  • urea resin phenolic resin, epoxy resin, soy protein glue, polyester, polyurethane, styrene acrylic emulsion, isocyanate, polyvinyl alcohol
  • urea resin phenolic resin
  • epoxy resin epoxy resin
  • soy protein glue soy protein glue
  • polyester polyurethane
  • styrene acrylic emulsion isocyanate
  • isocyanate polyvinyl alcohol
  • the raw materials for preparing the aforementioned profiles are cellulose-based materials and viscous polymer materials, and the mass ratio of cellulose-based materials and viscous polymer materials is 1: (0.01-100).
  • the mass ratio of the cellulose-based material and the viscous polymer material is 1: (0.1-10).
  • the mass ratio of the cellulose-based material and the viscous polymer material is 1: (0.3-2.0).
  • the viscous polymer material is one or more of natural viscous polymer materials and/or synthetic viscous polymer materials, and the natural viscous polymer material is acid-insoluble lignin or bio-based materials.
  • Calcium sulfonate the synthetic viscous polymer material is selected from polypropylene (PP), polyethylene (PE), polyvinyl chloride (PVC), polylactic acid (PLA), polyamide (PA), polyethylene terephthalate
  • PP polypropylene
  • PE polyethylene
  • PVC polyvinyl chloride
  • PLA polylactic acid
  • PA polyamide
  • PET diester
  • urea-formaldehyde resin phenolic resin
  • epoxy resin soy protein glue
  • polyester polyurethane
  • polyurethane styrene-acrylic emulsion and isocyanate.
  • the viscous polymer material comprises acid-insoluble Lignin
  • the viscous polymer material also contains other viscous polymers other than acid-insoluble lignin
  • the other viscous polymers other than acid-insoluble lignin are added with polyvinyl alcohol or bio-based Calcium sulfonate polypropylene, polyethylene or polyvinyl chloride; preferably, the viscous polymer contains acid-insoluble lignin contained in cellulose-based materials or acid added to cellulose-based materials Insoluble lignin, optionally, the viscous polymer also contains other viscous polymers other than acid-insoluble lignin, and it is particularly preferred that the viscous polymer material also contains inorganic nanomaterials.
  • the viscous polymer material is generally also described as "adhesive” or “glue”, and acidified lignin (or acid-insoluble lignin) is also used as a glue.
  • Polyvinyl alcohol and calcium biosulfonate have the effect of enhancing hydrogen bonding.
  • the addition of polyvinyl alcohol, calcium biosulfonate and other hydroxyl-rich polymers to the viscous polymer can form hydrogen bonds to improve strength, internal bonding and water resistance .
  • the bio-based calcium sulfonate is one of calcium cellulose sulfonate, calcium hemicellulose sulfonate, calcium starch sulfonate, calcium humate sulfonate, or calcium chitin sulfonate.
  • the bio-based calcium sulfonate is one of calcium cellulose sulfonate, calcium hemicellulose sulfonate, calcium starch sulfonate, calcium humate sulfonate, or calcium chitin sulfonate. Many kinds.
  • the isocyanate is toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), hexamethylene diisocyanate One or more of (HDI) or lysine diisocyanate (LDI).
  • the natural viscous polymer material or synthetic viscous polymer material is added in an amount of 10-80% of the mass of the profile (for example, composite profile or profile), so as to enrich the inter-skeletal unit in the pulp.
  • the amount of natural viscous polymer material or synthetic viscous polymer material is 10-50% of the mass of the profile (for example, composite profile or profile); preferably, the synthetic viscous polymer material is PVC ,
  • the addition amount is 20-50% of the mass of the profile (such as composite profile or profile), and 0.5-5% polyvinyl alcohol is added at the same time.
  • the cellulose-based material is pulp, paper product or plant skeleton.
  • the plant skeleton is a material that retains the basic shape or partial shape of the original plant body such as the root, stem, leaf and fruit, but the cell structure therein has been destroyed, part of the lignin and most of the intracellular chemical components in the cell have been lost and the shape is maintained.
  • bamboo blocks, bamboo chips, bamboo strips, wood chips, wood blocks, wood strips, plant stalks, plant fruit shells and other materials after treatment with acid, alkali, or oxidizing substances, part of the lignin is destroyed, and most of them The intracellular components are removed, but they still retain the original basic shape.
  • These materials are all referred to as plant skeletons in the present invention.
  • the cellulose-based material is a material that destroys plant cell walls through mechanical, physical or chemical processes, dissolves part of lignin and removes soluble cell components, and obtains a material that retains the natural skeleton structure of plants, which is called plant The skeleton, or splitting the plant skeleton to obtain the natural color pulp rich in cellulose, hemicellulose and lignin, or the natural color paper with a certain thickness further processed from the natural color pulp as the three basic raw material skeleton units.
  • the above-mentioned profile is a profile prepared by the following method:
  • the cellulose-containing plant material undergoes mechanical, physical or chemical processes to destroy plant cell walls, dissolve part of the lignin and remove soluble cell components to obtain plant unit materials that retain the natural skeleton structure, or split to obtain rich cellulose, hemicellulose, and
  • the natural color pulp of lignin, or the natural color paper with a certain thickness further processed from the natural color pulp is used as the three basic raw material skeleton units, and the three basic raw material skeleton unit plant unit materials, natural color pulp, and natural color paper are acidified, and/ Or add lignin salt (preferably sodium lignin) followed by acidification, and/or add acid-insoluble lignin recovered by acidification, and/or add viscous polymer material powder, and/or add viscous polymer film, and / Or adding a solution of viscous polymer, drying or paper, spreading or stacking, and hot pressing to obtain a series of new composite profiles or profiles.
  • lignin salt preferably sodium lignin
  • the above-mentioned cellulose-based material is a polysaccharide material that is processed by physical or chemical methods and is mainly linear high polymer plant cellulose and is rich in reticulated natural biopolymer lignin.
  • the cellulose in the material Some lignin molecules, some plant cell membrane components, some water-soluble components, alkali-soluble components and acid-soluble components in plant cells are removed from the lignin molecules, which exist in the form of pulp, paper products or plant skeletons.
  • the material is the cellulose-based material of the present invention.
  • the cellulose-based material is pulp
  • the pulp is a natural pulp rich in cellulose, hemicellulose and lignin; preferably, the natural pulp is pulped by an acid method or an alkali method.
  • the natural color paste prepared by the process preferably, the natural color paste is separated by alkali method and acidified precipitation to effectively remove the cell membrane and dissolve the cytoplasm. It has a micron length, is rich in cellulose, hemicellulose and lignin, and has natural viscosity. Natural color paste of polymer.
  • the production method of the pulp includes chemical pulping, mechanical pulping, semi-mechanical pulping, biological pulping or waste paper recycling pulping.
  • the pulp production method is non-chemical pulping, 5-60% acid-insoluble lignin or bio-based calcium sulfonate can be added to the pulp.
  • the chemical pulping is a pulping process that uses a clean process of precipitating lignin to produce natural color paste.
  • the pulp is plant raw material natural pulp, bleached pulp or recycled pulp.
  • the plant raw material natural color paste is bamboo and wood natural color paste with a water content of 40-70%, a pH of 9-10, and an acid-insoluble lignin content of 1%-50%.
  • the plant raw material natural color paste is prepared by a black liquor-free pulping process, and the cell membrane can be effectively removed and the cytoplasm can be dissolved and washed out by the alkali separation and acidification precipitation, and the high yield has one-dimensional structural characteristics.
  • a micron-length natural color paste that is rich in cellulose, hemicellulose and lignin, with natural viscous polymer acid-insoluble lignin.
  • the preparation process of plant raw material natural color paste can not only greatly reduce energy consumption and material consumption, but also effectively avoid environmental pollution, retain the macromolecular structure of natural lignin to the greatest extent, and provide a good solution for the development of bio-based materials and the extension of the industrial chain.
  • Original technology and raw material basis
  • the pulp further contains acid-insoluble lignin, wherein the sum of the mass of cellulose and hemicellulose accounts for 50%-90% of the mass of the pulp, and the mass of the acid-insoluble lignin accounts for the mass of the pulp The ratio is 1-80%.
  • the ratio of the mass of the acid-insoluble lignin to the mass of the pulp is 1-50%.
  • the ratio of the mass of the acid-insoluble lignin to the mass of the pulp is 10-80%.
  • the ratio of the mass of acid-insoluble lignin to the sum of the masses of cellulose and hemicellulose in the natural color paste of plant raw materials is (4-17): (73-89), and the ratio of acid-insoluble lignin
  • the sum of the mass of vegetarian, cellulose and hemicellulose accounts for 77-99% of the mass percentage of the plant raw material natural color paste.
  • the preparation method of the plant raw material natural color paste is: using an alkali with a mass concentration of less than 15% to treat the plant material at a temperature below 130°C to avoid the degradation of hemicellulose and lignin, and further rubbing and grinding
  • the pulp obtains a natural color pulp with a cellulose content of 40-80%, a hemicellulose content of 10-30% and a lignin content of 10-80%.
  • the plant material is bamboo, wood or plant straw.
  • the basis for calculating the mass percentage of the natural color paste is calculated based on the dry weight of the natural color paste.
  • the calculation basis of the proportion is involved.
  • the weight percentage of certain components is generally calculated on the basis of dry weight and solid weight.
  • the preparation method of the profile is: fully mixing the pulp and the viscous polymer material, and then pre-pressing, drying and hot pressing to prepare the profile.
  • adding acidified lignin or mixing into the pulp to synthesize The viscous polymer material makes it uniformly adsorbed and dispersed on the surface of the slurry, filtered, dried, and then spread, and hot-pressed to obtain a profile.
  • the product has flame retardancy; preferably, the acidified lignin is rich in lignin salt ( Preferably, the black liquor of sodium lignin), the synthetic viscous polymer material is a synthetic viscous polymer powder or a synthetic viscous polymer solution.
  • the mass ratio of the pulp to the viscous polymer material in the above profile is 1:9-9:1, and the temperature increases and the porosity decreases, the strength of the obtained profile is significantly improved, and the water resistance is increased; preferably, in the pulp Add 0.5-5% polyvinyl alcohol or bio-based calcium sulfonate. Adding polyvinyl alcohol or bio-based calcium sulfonate can make up for the weakening effect of the loss of binding water on the internal binding force of the material.
  • the present invention also provides a method for preparing the above profile.
  • the method is: fully mixing the cellulose-based material and the viscous polymer material, and then prepressing, drying and hot pressing to prepare the profile.
  • the The conditions of hot pressing are: temperature is 100-250°C, pressure is 1.5-20Mpa, and time is 5-60 minutes.
  • High-yield high-strength cellulose, hemicellulose and lignin can be obtained by kneading and refining.
  • the main component of the natural slurry is supplemented with a simple method of re-acidification of pulping black liquor rich in lignin salts (preferably sodium lignin), so that lignin can be uniformly adsorbed, precipitated and dispersed on the surface of the slurry, which is convenient for filtration.
  • lignin salts preferably sodium lignin
  • the one-dimensional pulp skeleton material is pavement and hot-pressed to obtain a new type of material with better performance than high-density board, and has good flame-retardant properties. Therefore, mixing resin or solution in the early stage of raw material filtration or drying can solve the problem of difficult dispersion in the later stage. Adding PVC and other synthetic plastic powders to the water-dispersed slurry solution can also achieve uniform dispersion, which is convenient for filtration. After drying, paving and hot pressing molding can also obtain high-performance composite profiles. Spraying synthetic resin powder or solution on the filtered fiber surface or air-dried state can also achieve a good dispersion effect.
  • the cellulose-based material is a paper product
  • the paper product is a paper product rich in cellulose, hemicellulose, and lignin
  • the paper product has a basis weight of 10- 400 g/m 2 and a thickness of 0.05-1.00 mm.
  • the paper product is a paper product derived from 60-150 g of plant raw materials.
  • both resin and plastic film are viscous polymer materials, viscous polymer materials with adhesive properties.
  • the paper-based material is paper or cardboard, which is also called a paper product.
  • the paper product is paper, paper scraps, paper chips, paper powder, and the like.
  • the paper product is one or more of virgin pulp board, corrugated surface paper, corrugated core paper or kraft paper; preferably, the paper product is a natural-color pulp board or a natural-color pulp paper; preferably, a paper product No surface coating, no filling, no sizing; preferably, the paper product is a paper product prepared by adding acid-insoluble lignin, synthetic viscous polymer powder or a solution of synthetic viscous polymer to the pulp, then papermaking and drying
  • the profile is isotropic, that is, the mutual difference ratio between the transverse static flexural strength and the longitudinal static flexural strength of the profile is less than 30%.
  • the amount of synthetic viscous polymer material added is 10-90% of the mass of the profile, and it is optimal to fill the gap between the paper product and the paper product. Especially preferably, the amount of synthetic viscous polymer material added is 10-50% of the mass of the profile.
  • the mass ratio of acid-insoluble lignin and cellulose in the paper product is (2-19): (34-68), and the sum of the mass of acid-insoluble lignin and cellulose accounts for the mass percentage of the paper product It is 77-99%.
  • the total mass of acid-insoluble lignin and cellulose accounts for 75-85% of the mass percentage of the paper product.
  • the paper product is 60-250 g/m 2 of paper derived from plant materials, or the paper product is 250-400 g/m 2 of paper derived from plant materials.
  • the paper product is a paper product obtained by adding a viscous polymer material to the pulp and then papermaking and forming.
  • the profile is prepared by the following preparation method: a paper product, a two-dimensional bio-based material, is used as a skeleton unit, and a synthetic viscous polymer film with adhesive function is alternately laminated and prepared by hot pressing.
  • Profiles or spray the paper product with a solution of viscous polymer or impregnate the paper product with a solution of viscous polymer, and then dry to obtain a treated paper product, and then stack the treated paper product or stack the treated paper product with the paper product alternately, Then heat press molding to prepare profiles; or add acid-recovered acid-insoluble lignin to the slurry, then make paper to obtain processed paper products, and then stack the processed paper products or alternately stack the processed paper products and paper products to release heat Press molding to prepare profiles; or add synthetic viscous polymer particles or a solution of synthetic viscous polymer to the slurry, and then make paper to obtain a processed paper product, and then stack the processed paper product or alternately stack the processed paper product and the paper product The exothermic press molding is used to prepare the profile.
  • adjacent paper products are crisscrossed along the paper flow pattern, adjacent adhesive polymer films crisscross along the transverse stretching direction, or the paper product and the adhesive polymer film are superimposed in the same direction.
  • the strength of the obtained profile will increase with the increase of the hot pressing temperature within the decomposition temperature of the main components, and decrease with the increase of the moisture content.
  • the preparation method of the profile is: using a paper product, that is, a two-dimensional bio-based material as a skeleton unit, and a viscous polymer film with the function of an adhesive, alternately stacked and hot-pressed to prepare the profile.
  • the polymer film is heated and pressed with the paper product to form a rivet structure, and is bonded and formed by physical bonding.
  • the moisture content of the paper product is 0.01% to 5%.
  • the thickness of the adhesive polymer film is 0.02-0.1mm, and the addition amount is 10-60% of the mass of the profile; preferably, the synthetic adhesive polymer film is PP film or PV film, and the synthetic adhesive polymer film The addition amount is 10-50% of the quality of the profile.
  • the preparation method of the profile is: spraying the paper product with a solution of viscous polymer or impregnating the paper product with a solution of viscous polymer, then drying to obtain a processed paper product, and then stacking the processed paper product Or, the treated paper product and the paper product are alternately stacked, and then thermocompressed to prepare a profile, and the concentration of the viscous polymer solution is 1-90% wt.
  • the preparation method of the profile is: adding acid-insoluble lignin recovered by acidification to the slurry, and then papermaking to obtain a processed paper product, and then stacking the processed paper product or combining the processed paper product with
  • the profile is prepared by staggered stacking and thermo-compression molding of the paper product, and the added amount of acid-insoluble lignin recovered by acidification accounts for 1-50% wt of the dry weight of the slurry.
  • the acid-insoluble lignin recovered by acidification is added to modify the synthetic viscous polymer and the strengthening effect of natural fibers, and the physical rivet structure is bonded and formed, and the acid-insoluble lignin recovered by acidification is used as the polyhydroxyl group.
  • the high-molecular viscous polymer enhances the hydrogen bond with cellulose, reduces the influence of water volume changes on the strength of the profile, and at the same time enhances the force between macromolecules in the plane and between the macromolecules in the longitudinal plane, so that the material strength, Toughness and internal cohesion increase synergistically.
  • the preparation method of the profile is: adding viscous polymer particles or a solution of viscous polymer to the slurry, and then papermaking to obtain a processed paper product, and then stacking the processed paper product or treating the paper The product and the paper product are alternately stacked and hot-pressed to prepare the profile.
  • the added amount of the viscous polymer particles is 5-150% of the mass of the slurry.
  • the added amount of the viscous polymer particles accounts for the slurry.
  • the mass percentage of the viscous polymer solution is 10-100%, the concentration of the viscous polymer solution is 1-99%wt, and the mass percentage of the dry matter in the viscous polymer solution to the dry mass of the slurry is 5-50% .
  • a solution mixed with viscous polymer powder or viscous polymer in the papermaking process can be used to achieve uniform dispersion of the resin on the surface and internal pores of the paper base, and better maintain the formation of hydrogen bonds in the paper base.
  • This paper-based skeleton structure can greatly reduce the amount of resin, reduce production costs, and produce cost-effective high-strength profiles.
  • the profile is isotropic, that is, the mutual difference ratio between the transverse static flexural strength and the longitudinal static flexural strength of the profile is less than or equal to 30%.
  • the difference between the transverse static flexural strength and the longitudinal static flexural strength of the profile is less than or equal to 30%, which means (transverse static flexural strength-longitudinal static flexural strength)/transverse static flexural strength ⁇ 30%, or (longitudinal static flexural strength- Horizontal static bending strength)/longitudinal static bending strength ⁇ 30%.
  • the mutual difference ratio between the transverse static flexural strength and the longitudinal static flexural strength of the profile is less than or equal to 20%.
  • the mutual difference ratio between the transverse static flexural strength and the longitudinal static flexural strength of the profile is less than or equal to 20%, which means (transverse static flexural strength-longitudinal static flexural strength)/transverse static flexural strength ⁇ 20%, or (longitudinal static flexural strength) Strength-horizontal static flexural strength)/longitudinal static flexural strength ⁇ 20%.
  • the profile prepared by the above method has isotropic profile, high strength and internal bonding force, low production cost, and is a new high-strength composite profile with a rivet structure.
  • the present invention also provides a method for preparing the above-mentioned profile, which is prepared by using a paper product, that is, a two-dimensional bio-based material as a skeleton unit, and a synthetic viscous polymer film with the function of an adhesive.
  • Profiles or spray the paper product with a solution of viscous polymer or impregnate the paper product with a solution of viscous polymer, and then dry to obtain a treated paper product, and then stack the treated paper product or stack the treated paper product with the paper product alternately, Then heat press molding to prepare profiles; or add acid-recovered acid-insoluble lignin to the slurry, then make paper to obtain processed paper products, and then stack the processed paper products or alternately stack the processed paper products and paper products to release heat Press molding to prepare profiles; or add viscous polymer particles or viscous polymer solutions to the slurry, and then make paper to obtain processed paper products, and then stack the processed paper products or alternately stack the processed paper products and paper products to release heat
  • the profile is prepared by compression molding, wherein the mass ratio of the paper product and the viscous polymer is 1: (0.1-1.0), and the paper product is a paper product rich in cellulose, hemicellulose, and lignin; preferably, the paper product
  • the preparation slurry of the paper product is a natural color slurry
  • the natural color slurry is processed with low alkali content and low temperature to prevent the degradation of hemicellulose and lignin, and further rubbing and kneading Refining to obtain a natural color paste containing cellulose, hemicellulose and lignin.
  • the synthetic viscous polymer material is added in an amount of 10-90% of the mass of the profile, and it is optimal to fill the gap between the paper product and the paper product.
  • the added amount of synthetic viscous polymer material is 10-50% of the mass of the profile
  • the paper product is 60-250 g/m 2 of paper derived from plant materials, or the paper product is 250-400 g/m 2 of paper derived from plant materials.
  • the paper product is prepared by adding a viscous polymer material to the pulp and then forming a paper product.
  • the moisture content of the paper product is 0.01% to 5%.
  • the thickness of the viscous polymer film is 0.02-0.1mm, and the addition amount is 10-60% of the mass of the profile; preferably, the synthetic viscous polymer film is PP film or PV film, viscous polymer The added amount of the material film is 10-50% of the mass of the profile.
  • the added amount of acid-insoluble lignin recovered by acidification accounts for 1-50%wt of the dry weight of the slurry.
  • the added amount of the viscous polymer particles is 5-150% by mass of the slurry, the concentration of the viscous polymer solution is 1-99%wt, and the viscosity
  • the weight percentage of the dry matter in the polymer solution to the dry matter of the slurry is 5-150%.
  • the weight percentage of the dry matter in the viscous polymer solution to the dry matter of the slurry is 10-100%.
  • the paper product is prepared by the following method: acid-insoluble lignin is precipitated by acidification during a clean pulping process or a post-treatment process, or acid-insoluble lignin is supplemented, or viscosity is supplemented Polymer powder, or supplemented with viscous polymer solution, and then papermaking and forming to obtain paper products.
  • the hydrogen bond formed by the intramolecular and intermolecular hydrogen bonds of the fiber bundles and the bound water serves as the basis of the internal binding force, so that the paper product becomes a plane with a network structure and a certain strength. Two-dimensional paper-based material.
  • the acid-insoluble lignin on the surface of the paper product can enhance the bonding force between the paper base and the resin.
  • the addition of viscous polymer materials, such as polyvinyl alcohol or bio-based sulfonate, can reduce the lack of high-temperature binding water.
  • the internal bonding force and strength of the product are reduced, and a new high-strength material with a rivet structure can be obtained by immersing a viscous polymer liquid or laminating and hot pressing with a viscous polymer film.
  • the above profiles utilize the strong hydrogen bonds between the hydroxyl groups of cellulose, hemicellulose and lignin to make paper products have good internal binding force and mechanical strength. Adjusting water, polyvinyl alcohol, bio-based sulfonate, etc. can further strengthen the paper.
  • the internal bonding force of the product has good basic strength.
  • a two-dimensional plane kraft paper with an interpenetrating network structure is used as the structural unit
  • a multi-layer staggered stack of kraft paper is used as the basic skeleton layer structure of the profile
  • viscous polymer materials such as synthetic resin or finished plastic film are used as viscose.
  • the adhesive through hot pressing and melting, makes the viscous polymer material fully fill the gaps between the fibers of the paper product, forming a new high-strength material with a rivet structure. Because paper products have acid-insoluble lignin inside and on the surface, and acid-insoluble lignin on the fiber surface can improve the interface compatibility with synthetic materials and enhance the binding force.
  • the cellulose-based material is a plant skeleton
  • the plant skeleton is a sheet-like plant material obtained by sequentially undergoing lye treatment and acid treatment
  • the viscous polymer is a plant skeleton
  • the natural viscous polymer material retained in the acid-insoluble lignin, or the viscous polymer is a synthetic viscous polymer material and the natural viscous polymer material retained in the plant skeleton.
  • the above-mentioned profile is a high-strength lightweight "bamboo steel" with the natural plant skeleton as the three-dimensional structural unit and the natural acid-insoluble lignin or synthetic resin as the adhesive.
  • Building weight reduction, enhancement and anti-corrosion is the development direction of the industry. Instead of large-weight steel bars, the use of lightweight composite materials is the development direction of building materials. Natural bamboo and wood have good strength. Due to their compactness, strength and structural defects, they cannot meet the requirements of building reinforcement materials.
  • the invention adopts the idea of not damaging the skeleton structure of plant raw materials, so as to fully retain the mechanical properties of the bamboo/wood material itself. After repeated experiments and explorations, a "bamboo steel" product (hereinafter referred to as "profile” in the invention) and technology based on the natural skeleton of bamboo has been successfully developed.
  • the strength of bamboo steel products can reach 400MPa and the elastic modulus It can reach 33000Mpa.
  • the cellulose-based material is a plant skeleton
  • the plant skeleton is a sheet-like plant material obtained by sequentially undergoing lye treatment and acid treatment
  • the viscous polymer is retained in the plant skeleton.
  • the natural viscous polymer material is acid-insoluble lignin
  • the viscous polymer is a synthetic viscous polymer material and the acid-insoluble lignin retained in the plant skeleton.
  • the method for preparing the profile is: sequentially subjecting the sheet-like plant material to lye treatment and acid treatment to obtain the plant skeleton and hot pressing to prepare the profile.
  • the lye is treated before the acid treatment
  • the sheet-like plant material is immersed in a saturated lignin salt (preferably sodium lignin) solution, and the hot pressing process is: according to the selected polymer material, hot pressing at a temperature of 3-20Mpa above 100°C for 15 minutes- 24 hours.
  • a saturated lignin salt preferably sodium lignin
  • the preparation method of the plant skeleton is: processing the plant material into a sheet with an average width of 1-5 cm and a length according to the processing requirements, soaking it in a NaOH solution with a concentration of 1%wt or more, and After cooking for 1-10h at less than 130°C, the cell membrane is fully destroyed and the lignin and soluble cell components are dissolved out, and the structural unit that still maintains the flaky structure and the internal pores is obtained.
  • the structural unit is re-immersed in the saturated lignin salt (preferably Sodium lignin) solution to absorb as much as possible, and then take it out and soak into the dilute acid solution for full acidification or directly soak the structural unit into the dilute acid solution for full acidification, and then wash to remove salt and small molecular organic matter, and dry the water to obtain the plant skeleton
  • the saturated lignin salt preferably Sodium lignin
  • the plant material is bamboo, wood or straw, and preferably, the bamboo is a bamboo material obtained from 3-5 years of adult bamboo.
  • the plant skeleton is subjected to hot alkali liquor cooking treatment and acidification washing and drying to obtain a modified three-dimensional sheet with a certain amount of acid-insoluble lignin in the pores of the plant skeleton.
  • the preparation method of the profile is as follows: the sheet-shaped plant material is subjected to lye treatment and acid liquid treatment to obtain the plant skeleton, and then a synthetic viscous polymer material is added and hot pressed to prepare the profile.
  • the hot pressing process is: according to the selected polymer material, hot pressing at 3-20 Mpa above 100° C. for a time of 15 minutes to 24 hours.
  • the viscous polymer material is a reactive isocyanate, or polypropylene, polyethylene or polyvinyl chloride added with polyvinyl alcohol, wherein the polyvinyl alcohol has enhanced hydrogen Key role.
  • the natural viscous polymer acid-insoluble lignin or synthetic viscous polymer material is added in an amount of 10-70% of the mass of the profile, and it is optimal to just fill the voids of the skeleton unit; preferably, synthetic viscous polymer
  • the addition amount of the material is 20-50% of the mass of the profile.
  • the viscous polymer is a synthetic viscous polymer material, 0.5-5% of the mass of the profile is added at the same time to improve the strength and internal bonding force.
  • the viscous polymer is natural acid-insoluble lignin, phenolic resin, urea-formaldehyde resin, PP, PVC, PVA.
  • the mass ratio of acid-insoluble lignin to the dry weight of the treated bamboo chip is (1-20): (70-95), and the sum of the mass of acid-insoluble lignin and cellulose accounts for the mass percentage of the profile 75-99%.
  • the method for preparing the profile is: destroying the cell membrane of the long-size sheet by steaming with a hot alkali solution to open up the channel between plant cells, dissolve lignin and soluble cell components, and maintain the internal cavity and original shape.
  • the present invention also provides a method for preparing the above-mentioned profile.
  • the preparation method comprises: sequentially subjecting the sheet-like plant material to alkali solution treatment and acid solution treatment to obtain a plant skeleton and hot pressing to prepare the profile, or, sequentially passing the sheet-like plant material through Alkali solution treatment and acid solution treatment are used to obtain plant skeletons, and then synthetic viscous polymer materials are added to prepare profiles by hot pressing.
  • the hot pressing process is: hot pressing at a temperature of 100°C or higher, 3-20Mpa, and the time is 15 minutes-24 hours .
  • the present invention also provides the use of the above-mentioned profile, which is characterized in that the profile is used as a substitute for supporting structure materials, reconstituted bamboo/wood, metal steel, high-density fiberboard, wood-plastic materials or plastics.
  • the outer layer of the profile can be coated with functional materials such as flame-retardant, waterproof, metal, and veneer decoration materials.
  • the profile is used as a substitute for high-density fiberboard, wood-plastic material or plastic.
  • the present invention also provides the use of the above profile, which is characterized in that the profile is used to make support structure materials, restructured bamboo/wood, metal steel, high-density fiberboard, wood-plastic materials or other composite materials.
  • the present invention solves the series of problems such as difficult dispersion of cellulose in composite fiber materials, small addition amount, low strength, high bending stress, easy deformation, anisotropy, formaldehyde pollution and poor flame retardancy, etc., and achieves a significant reduction in production costs and a large Improve the strength and toughness of composite materials, and can produce safe and environmentally friendly high-density fiberboards that are much stronger than natural materials such as plastics and wood-plastic materials.
  • the beneficial effect of the present invention is that it is the first to use kraft paper as the two-dimensional basic structural unit and framework material, and use natural lignin and synthetic viscous polymer materials as the bonding material to produce high strength and high strength through hot pressing.
  • the simple and efficient method of cost-effective new materials and their products realize the low-cost, high-performance new composite materials with bio-based materials as the main body, which greatly reduces the amount of resin or plastic. Its strength, toughness and internal binding force greatly exceed those of natural materials.
  • Materials, plastics, plastic fiber composite materials, and high-density fiberboard have solved the series of problems such as difficult dispersion of fibers in plastic resin, small addition amount, and large decrease in strength.
  • the profile product of the present invention uses paper-based material as the main raw material, and the paper-based material is a paper product.
  • the amount of resin is appropriate, its strength can reach 1-15 times the strength of a plastic product.
  • the invention also opens up a new way for high value-added utilization of biomass raw materials such as orange stalks, bamboo and wood, and solves the problems of existing composite materials such as difficult dispersion of fibers, inability to add large amounts, low product strength and poor toughness, and significant advantages in raw materials and cost performance.
  • biomass raw materials such as orange stalks, bamboo and wood
  • problems of existing composite materials such as difficult dispersion of fibers, inability to add large amounts, low product strength and poor toughness, and significant advantages in raw materials and cost performance.
  • the invention uses chemical principles and methods to destroy plant cell membranes, remove part of lignin and soluble organic small molecules, open up the internal channels of the three-dimensional material organization, retain the original shape and structure of bamboo/wood strips, eliminate the interference of salt and small molecules, and then immerse and saturate
  • the lignin salt preferably sodium lignin
  • synthetic resin solution or melt can more effectively fill the gaps of the three-dimensional framework, reduce material gaps, increase specific gravity, and overcome the lack of binding force in the existing recombinant bamboo, the pores are difficult to eliminate, and the strength is difficult
  • hot press molding can obtain denser and high-strength composite profiles. And the product performance is significantly better than that of reconstituted bamboo, the strength exceeds that of steel, and the light green bamboo steel or bamboo profile with natural corrosion resistance and flame retardant properties.
  • the reason for the significant increase in the strength and internal bonding force of this new material system is that the non-polar polymer viscous polymer powder is closely combined with the fiber unit through hot pressing and melting, filling the pores to the greatest extent, and the coverage of lignin on the fiber surface can be increased.
  • the lipophilicity and the strength of fiber materials promote the mutual solubility with viscous polymers.
  • Polyhydroxyl groups in fiber crystals, hemicellulose and lignin macromolecules can form a hydrogen bond network with each other. Free polyhydroxyl groups such as water molecules and polyvinyl alcohol are large. Molecules are beneficial to increase the inter-molecular binding force and increase the strength of the profile.
  • Fig. 1 is a schematic diagram of a three-dimensional structure of a pulp skeleton substrate of a PVC-fiber composite material in a preferred embodiment of the present invention.
  • Figure 2 is the physical picture of the PVC-fiber-based composite material.
  • Fig. 3 is a graph showing the mechanical strength performance of the resin-fiber-based composite material of the present invention.
  • FIG. 4 is a schematic diagram of the three-dimensional structure of the paper skeleton substrate of the resin-paper-based composite material in a preferred embodiment of the present invention.
  • Figure 5-A is a graph of the mechanical strength performance of the resin-paper-based composite material of the present invention.
  • Figure 5-B is a comparison diagram of the mechanical strength performance of the pure resin and the resin-paper-based composite material of the present invention.
  • Figure 5-C is a graph of the internal bonding strength and the 24-hour water absorption thickness expansion rate of the resin-paper-based composite material of the present invention.
  • Figure 6-A is an electron micrograph of a commercially available 80g/m 2 kraft paper.
  • Figure 6-B is an electron micrograph of a PP-paper-based composite material with a commercially available 80g/m 2 kraft paper as the raw material and 20% PP addition.
  • Figure 7-A is an electron microscope image of 70g/m 2 kraft paper.
  • Figure 7-B is an electron micrograph of PP-paper-based composite material with 70g/m 2 kraft paper as raw material and 38% PP addition.
  • Figure 8-A is an electron microscope image of 70g/m 2 kraft paper, which is the same as Figure 7-A. This image is repeatedly placed to enhance the contrast.
  • Figure 8-B is an electron micrograph of a PVC-paper-based composite with 70g/m 2 kraft paper as raw material and 28% PVC addition.
  • Figure 8-C is an electron micrograph of a PVC-paper-based composite with 70g/m 2 kraft paper as raw material and 33% PVC addition.
  • Figure 8-D is an electron micrograph of a PVC-paper-based composite with 70g/m 2 kraft paper as raw material and 45% PVC addition.
  • Figure 9-A is a graph of the relationship between the mechanical strength of the PP-paper-based composite material, the proportion of PP addition, and the hot pressing temperature.
  • Figure 9-B is a graph of the relationship between the mechanical strength of PVC-paper-based composites, the proportion of PVC addition, and the hot pressing temperature.
  • Figure 9-C is a diagram showing the relationship between the mechanical strength of PA-paper-based composites, the ratio of PA addition, and the hot pressing temperature.
  • Figure 9-D is a graph of the relationship between the mechanical strength of the PA-paper-based composite and the type of paper-based.
  • Figure 10-A is an electron micrograph of the original bamboo longitudinal.
  • Figure 10-B is a longitudinal electron micrograph of bamboo steel (magnification 150 times), showing that both the fiber bundles and parenchyma cells are compacted.
  • Figure 10-C is a longitudinal electron micrograph of bamboo steel (magnification 700 times), showing that the linear fiber bundles are arranged neatly and very densely.
  • Figure 10-D is a longitudinal electron micrograph of bamboo steel (magnification 800 times), showing that the fiber bundles are very dense.
  • Figure 11 The relationship between the mechanical properties of the bamboo steel of the present invention and the lignin content.
  • 8.1%/PVA refers to the addition of lignin and PVA to the composite material, where the addition ratio of lignin is 8.1%, and the addition ratio of PVA is 2%.
  • the thickness of the profile is within 3.5 mm.
  • the bamboo slices are boiled at 75°C for 10-12h with a concentration of 13% NaOH solution. After rubbing and grinding, a green natural bamboo pulp with a water content of 60% and a pH of 9-10 is obtained. It is acidified to pH with 2% dilute sulfuric acid. For 2-3, wash with clean water, sieve the pulp, and dissolve it through a fiber decomposer, and prepare a slurry with a pulp concentration of 1% for use.
  • the mass content of cellulose (containing hemicellulose) in the natural bamboo pulp (based on dry weight) after acidification was measured to be 58.98%, and the content of acid-insoluble lignin was 23.96%.
  • the PVC addition amount is only 31.01%
  • the hot pressing condition is 185°C, 10MPa
  • the static bending strength of the PVC-pulp composite material is 62.15MPa
  • the elastic modulus is 5235MPa
  • the water absorption thickness expansion rate is 24h 8.10%
  • the results are better than the requirements of static flexural strength (42.0MPa), elastic modulus (3800MPa) and 24h water absorption thickness expansion rate (12.0%) of high-humidity high-density fiberboard described in GB/T 31765-2015.
  • the pulping method is the same as Step 1 of Example 1 above.
  • the pulp skeleton base material is hot-pressed, pressure-maintained and cooled to obtain the product.
  • the specific hot-pressing conditions and profile properties are shown in Table 3.
  • the mass ratio of the sum of the viscous polymer PVA and acid-insoluble lignin to cellulose is about 0.85 (the mass ratio of cellulose to viscous polymer is about 1.18 ), even if 10% of nano-calcium-based materials are added, its static flexural strength and elastic modulus are far better than those of ordinary high-density fiberboard described in GB/T 31765-2015 (38.0MPa), Elastic modulus (3900MPa) requirements.
  • the content of cellulose and acid-insoluble lignin in the natural bamboo pulp is the same as in Example 1, and the addition amount of styrene-acrylic emulsion and the addition amount of calcium cellulose sulfonate are calculated based on the solid content.
  • the percentage content of the emulsion is the percentage content of the original color paste
  • the calcium cellulose sulfonate is the percentage content of the total mass of the dry matter of the raw material of the profile.
  • the mass ratio of the total mass of calcium sulfonate and acid-insoluble lignin in the natural color paste to cellulose is 0.59-1.25 (the mass ratio of cellulose and viscous polymer is 0.80-1.71).
  • the mass ratio of cellulose and viscous polymer in the profile is 0.80-1.71, the static flexural strength and elastic modulus of the material are far superior It meets the requirements of ordinary high-density fiberboard static bending strength (38.0MPa) and elastic modulus (3900MPa).
  • paper pulp is used as the raw material of micro-nano fibers
  • lignin or synthetic resin precipitated by acidification is used as the bonding agent.
  • Various new composite profiles with static bending strength of 45-120MPa are produced by hot press molding, which are better than the national standard wet For the requirements of static flexural strength (42.0MPa) and elastic modulus (3900MPa) of high-density fiberboard, please refer to Figure 3.
  • the paper skeleton base material is hot-pressed, pressure-maintained and cooled to obtain the product.
  • the mass of the paper base is 50-90% and the content of PP plastic is 10-50%, that is, the sum of the mass of acid-insoluble lignin in PP plastic and kraft paper (total mass of viscous polymer) and kraft paper
  • the mass ratio of cellulose is 0.22-1.39 (the mass ratio of cellulose and viscous polymer is 0.72-4.52)
  • the hot pressing time is 15-20 minutes
  • the hot pressing temperature is 175-195°C
  • the pressure is 5-8MPa.
  • the prepared profile has a static bending strength of 45-92MPa and an elastic modulus of 4000-13237MPa.
  • the PP addition amount is 20%
  • the hot pressing condition is 190°C, 8MPa
  • the static flexural strength of the PP-paper-based composite material hot pressed for 15 minutes is 92.52MPa
  • the elastic modulus is 13124MPa. It is far better than the requirements of ordinary high-density fiberboard for static bending strength (38.0MPa) and elastic modulus (3900MPa).
  • the profile can maintain the static flexural strength and elastic modulus of the profile.
  • the static flexural strength of the material will increase when the moisture content is increased.
  • the modulus of elasticity will decrease.
  • the paper skeleton base material is hot-pressed, pressure-maintained and cooled to obtain the product.
  • the performance of the product under various conditions is shown in Table 8-10.
  • the amount of PP added is 22.10%, and the mass ratio of the sum of the acid-insoluble lignin in PP and kraft paper (total mass of viscous polymer) to the mass ratio of cellulose in kraft paper is 0.89 (the mass ratio of cellulose to viscous polymer is 1.13 , Where PP is a viscous polymer, and the acid-insoluble lignin in kraft paper is also a viscous polymer), through hot pressing conditions of hot pressing 7MPa, hot pressing for 15 minutes, and hot pressing temperature from 180-210°C to prepare PP-paper base
  • the strength of the composite material does not change much with temperature, which is better than the static bending strength (42.0MPa) and elastic modulus (3900MPa) requirements of wet high-density fiberboard.
  • the hot pressing condition is 7MPa, 210°C hot pressing for 15 minutes, when the PP addition is more than 27.98%, the material performance is far better than the static bending strength (42.0MPa), elastic modulus (3900MPa) and internal bonding force of the wet high-density fiberboard (1.20MPa), the requirement of water absorption thickness expansion rate (16.0%).
  • the synthetic viscous polymers are PP and PVA
  • PP and PVA are used as synthetic viscous polymers
  • the acid-insoluble lignin in kraft paper is used as the natural viscous polymer
  • the total mass of the viscous polymers (PP+PVA+acid-insoluble lignin)
  • the mass ratio of cellulose to kraft paper is 0.89, 1.00, 1.15 (the mass ratio of cellulose to viscous polymer is 1.13, 1.00, 0.87)
  • the prepared profiles are better than wet high-density fiberboard static bending strength ( 42.0MPa), elastic modulus (3900MPa) requirements.
  • the hydrogen bonding effect is increased, and the strength is improved significantly.
  • the static bending strength increased by 43.88%
  • the elastic modulus, and the internal binding force increased significantly.
  • 25 sheets of paper 1 and film 2 are alternately stacked vertically and horizontally to obtain a paper skeleton substrate of a resin-paper-based composite material.
  • the paper skeleton base material is hot-pressed, pressure-maintained and cooled to obtain the product.
  • the properties of the material obtained under various conditions are shown in Table 11.
  • the tensile strength at °C is 71.76MPa
  • the static flexural strength is 120.38MPa
  • the modulus of elasticity is 8280.80MPa
  • the thickness expansion rate of 24h water absorption is 13.97%, which is much better than the static flexural strength (42.0MPa) and elastic modulus of wet high-density fiberboard.
  • the requirement for the mass (3900MPa) is 2.4 times the tensile strength (29.4MPa) of UPVC, 2.64 times the static flexural strength (45.6MPa), and 2.75 times the elastic modulus of rigid PVC (1500-3000MPa).
  • the profiles prepared with serial numbers 1, 4, and 5 also meet the requirement of 24h water absorption thickness expansion rate (16.0%).
  • the paper skeleton substrate of HDPE-paper-based composite material and the paper skeleton substrate of PLA-paper-based composite material are hot-pressed and pressure-maintained to cool down to obtain products.
  • the specific properties are shown in Tables 12 and 13.
  • the static flexural strength and elasticity of the HDPE-paper-based composite material in Table 12 (the mass ratio of cellulose to viscous polymer is 2.03) and the PLA-paper-based composite material in Table 13 (the mass ratio of cellulose to viscous polymer is 0.77)
  • the modulus performance is better than the requirements of ordinary high-density fiberboard static bending strength (38.0MPa) and elastic modulus (3900MPa).
  • the HDPE-paper-based composite material prepared by the criss-crossing processing method of adjacent paper bases is isotropic, and the static flexural strength and elastic modulus performance in the horizontal and vertical directions are better than the static flexural strength of ordinary high-density fiberboard (38.0MPa), Elastic modulus (3900MPa) requirements.
  • the paper skeleton base material is hot-pressed, pressure-maintained and cooled to obtain the product.
  • the specific properties are shown in Table 14.
  • the spraying method is used to control the sizing ratio, and 50 sheets of paper 1 are stacked in a crisscross pattern.
  • the paper skeleton base material is hot-pressed and pressure-maintained and cooled to obtain the product urea-formaldehyde-paper-based composite material, and the specific properties of MDI-paper-based composite material are shown in Table 15.
  • the mass ratio of cellulose to viscous polymer is 4.52, indicating that the reactive MDI can make the profile have higher static flexural strength and internal bonding strength at a lower addition amount, and can be used as a composite Component.
  • 25 sheets of paper 1 and film 2 are alternately stacked vertically and horizontally to obtain the paper skeleton substrate of the PA-paper-based composite material.
  • the paper skeleton base material is hot-pressed, pressure-maintained and cooled to obtain the product. See Table 16 for specific properties.
  • the static flexural strength at 235°C is 135.12MPa
  • the elastic modulus is 9608MPa
  • the thickness expansion rate of 24h water absorption is 14.63%
  • the strength is much better than the static flexural strength (42.0MPa) and elastic modulus (3900MPa) requirements of wet high-density fiberboard.
  • the thickness expansion rate (16.0%) of water absorption in 24h also meets the requirements.
  • the resin addition rate increases; at the same time, because the fiber and the resin are incompatible, the resin addition rate will overflow if the resin addition rate is too high; the paper base thickness or too thin, the mechanical properties decrease.
  • the performance of the composite material of strong polar PVC and PA is better than that of non-polar resin PP composite material.
  • Cellulose is a hydrophilic polymer. It is the polar material lignin that can interact with PVC and PA, so it contains wood.
  • the plain cellulose paper base as the base material uses simple processing methods to strengthen the advantages of each raw material.
  • the resin addition rate of 30% is far better than that of the same materials, and the cost is low. problem.
  • the bamboo chips were subjected to hot pressing at 100°C and 5MPa for 24 hours, cooled naturally, and placed at room temperature for 36 hours, and then the mechanical properties were measured, as shown in Table 17.
  • the blank is the tensile strength and elastic modulus properties of the treated bamboo slices, which are acidified after alkali hydrolysis to form a three-dimensional bamboo material containing acid-insoluble lignin (the ratio of cellulose content to acid-insoluble lignin content) 2.5-14.9), after hot pressing, bamboo steel with tensile strength close to 400MPa and strength exceeding steel Q235 can be obtained.
  • the acidified bamboo strips are cleaned in boiling water and dried naturally until the moisture content is 30% for later use.
  • the blank is the performance of untreated bamboo strips to directly measure the static flexural strength and elastic modulus.
  • the serial number is the static flexural strength of the profile obtained by hot pressing after acidification after alkali hydrolysis and without adding glue.
  • No. 2-4 is a profile prepared after adding phenolic formaldehyde (the ratio of cellulose content to viscous polymer content is 1.3-1.7), and its impact toughness is improved compared to the original bamboo strips.
  • the elastic modulus is 18000 MPa
  • the static bending strength reaches 160 MPa, which is a superior product.
  • the static bending strength of No. 4 product is 188.94 MPa, which is 1.18 times that of the recombined bamboo superior product.
  • the acidified bamboo strips are cleaned in boiling water and dried naturally for later use.
  • step 4 Dry the bamboo slices of step 2 and step 3 at 180°C for 20 minutes, arrange the single layer into a 150mm*200mm size, and place them in a mold, then place them in a mold at 230°C and 7MPa radial compression for 30 minutes, cool naturally, and place them at room temperature for 36 hours.
  • Performance measurement (cellulose content and viscous polymer ratio is 2.2-10.5), the results are shown in Figure 11. It can be seen that the static flexural strength (marked as the bending strength in the figure) of the material prepared by this method is 199-306MPa, the elastic modulus is greater than 18GPa (that is, 18000MPa), and the impact toughness is 12.06-15.30KJ/m 2 .
  • Moso bamboo strips selected from the factory, length 2100.0mm; width 25.0mm; thickness 3.0mm. Place it in a 5% NaOH solution at 95°C for 3 hours and bake until the moisture content is less than 10%.
  • the moso bamboo strips treated in step 1 are processed in accordance with the conventional process of reconstituted bamboo, with Steyr glue 10%, dried for 3-4 hours at ⁇ 50°C, and moisture content ⁇ 10%. Take 85kg of the treated bamboo bundle and mold it along the fiber direction. Hot press molding under the conditions of 140-145°C, 6MPa, 30min.
  • the product obtained by trimming (the ratio of cellulose content to viscous polymer content is 1.6) is: length 1850mm, width 140mm, thickness 18mm, measured in accordance with the GB/T 17657-2013 method, and the product density is 1.33g/cm 3.
  • the static bending strength is 161MPa (deep carbon plate ⁇ 70MPa), the elastic modulus is 15739MPa, and the water absorption thickness expansion rate is 4%.
  • the main properties such as density, mechanics and waterproof of the product created by the invention all meet the requirements of the national standard GB/T30364, and the static bending strength is 2.3 times that of the national standard.

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Abstract

一种生物质重组型材，用物理或化学制浆工艺破坏细胞壁，去除部分木质素及可溶性细胞成分，获得天然骨架结构或拆分获得富含纤维素、半纤维素及木质素的本色浆或由本色浆进一步加工成有一定厚度的本色纸作为三大基础原料骨架单元，通过补加酸化回收木质素或添加合成材料粉体或薄膜或溶液作为粘结剂，经烘干或成纸，铺装或叠放，热压成型得到复合型材或异型材。通过生物质天然骨架或成纸前浆料中添加粘性聚合物实现纤维原料与粘胶剂均匀混合；或成品纸施胶后烘干或与塑料薄膜交错复卷；借助连续化造纸生产工艺与热压成型工艺，大规模、低成本、高性价比生产以生物基材料为主的管材、板材和异型材。还包括一种型材的制备方法。

Description

一种生物质重组的型材及型材的制备方法 技术领域
本发明涉及生物基复合材料领域，具体的，涉及一种生物质重组的型材及型材的制备方法。
背景技术
生物质新材料是人类未来发展的根本方向，最能满足环境、动物/人类健康，使用安全，符合可持续发展要求。生物质原料丰富，木或竹用作建筑和家具已有数千年。竹、秸秆等生物质由于尺寸大小不一，结构、密度均一性差，各向异性，存在结和生长缺陷，利用率一直不高。我国古代四大发明之一的造纸术克服了上述难题，实现了将植物原料用碱法拆分为规格统一为毫米级本色浆的重大技术突破，为生物质重组成型提供了技术和产业基础。但生产的纸制品强度非常低；纤维原料加入脲醛树脂或酚醛树脂等胶粘剂热压而成的纤维板存在强度低、性能差和甲醛危害问题。将植物原料中木质素完全脱除得到纳米纤维素晶体，基于纳米纤维素“模块”可构建系列纤维素基高分子材料可大幅提高强度，但工艺复杂、生产成本高、用途受限。近年来发展起来的采用机械法疏解竹材，通过烘干，浸渍酚醛树脂再烘干热压的工艺可得到力学性能比原竹增加2-3倍的重组板材或方材，是竹/木加工的技术突破。由于粘胶剂难以充满细胞，存在影响粘接力的其他小分子，弯曲应力大，易变形，各向异性问题仍未能克服，强度提升有限，人工处理单竹片的生产加工方式设备投资大，劳动密集，产效率低，加工成本高，自动化水平低，难以规模化生产。因此生物质加工重组技术有待突破。
以纤维粉为填料的纤维塑料复合材料加工方式同样存在塑料强度下降幅度大、产品韧性差、添加量少等问题。纤维与塑料为主要成分的木塑材料的热压成型和共混挤出成型技术虽然生产过程简单，周期短、效率高、产品质量稳定、生产成本较低，但天然纤维中的纤维素、半纤维素大分子、木质素大分子中含有大量强极性的羟基和醚键，容易团聚，与聚乙烯(PE)，聚丙烯(PP)，聚氯乙烯(PVC)等热塑性非极性或弱极性聚合物混融性差，难分散，流动性差，难加工，力学性能特别是韧性不高等系列影响木塑材料发展的技术难题需要破解。
专利文献CN1168591C中公开了聚合物与纤维素纤维的复合物制备得到的复合材料，最终复合材料中包含30-40％的纤维，其中聚合物为PP、LDPE、HDPE、PS，纤维素纤维为一年生植物纤维或韧皮纤维，例如亚麻、大麻、黄麻和洋麻等，也可采用纸纤维，但是制备得到的纤维板无法达到普通纤维素板的要求。
CN107000383A公开了多层夹层结构，在两层聚合物层中间夹层纤维素酯层，纤维素酯 可以为乙酸纤维素、乙酸丙酸纤维素、乙酸丁酸纤维素、纤维素三乙酸酯、纤维素二乙酸酯、纤维素三丙酸酯、纤维素三丁酸酯、及其混合物，该夹层结构可用于制造具有高硬挺度且具备用于各种应用的良好光学透明度的玻璃面板。
因此，利用来源广泛、绿色环保、成本低廉的植物原料、加工剩余物及合成树脂生产性能优良、成本低廉的复合材料很有价值。
发明内容
本发明就是为了充分发挥竹/木材料分拆的本色浆自身的高强度力学性能，破解人造纤维板强度低，木塑材料难混合，纤维材料添加量低，树脂与纤维材料难以混合均匀及高温热压水份丢失影响强度等系列问题，解决脲醛树脂、酚醛树脂及大豆蛋白树脂粘结剂强度低，甲醛毒性等系列生物基复合材料使用中的问题，开发强度高、绿色环保、阻燃性能好的粘胶剂及生物基材料及重组成型新技术。
本发明所述高密度板对比参考国家标准GB/T 31765-2015,产品试件尺寸，密度，含水率，拉伸强度，静曲强度(弯曲强度)和弹性模量(三点弯曲，或者称为弯曲模量)，冲击韧性，内结合强度，24h吸水厚度膨胀率性能检测均采用国家标准GB/17657-2013中所述方法。
为此，本发明开发了一种新型复合型材，其特征在于所述型材包含纤维素和粘性聚合物，所述型材的静曲强度为40-500MPa，弹性模量为4000-40000Mpa，纤维素和粘性聚合物的质量比为1：(0.01-100)。
其中纤维素是D-葡萄糖以β-1,4糖苷键结合起来的链状高分子聚合物。
其中粘性聚合物是具有粘性的高分子聚合物，所述高分子聚合物在常温或加热的情况下能够实现粘黏特性，或者在有机溶剂或水作为溶剂的情况下具有粘黏特性。
优选的，上述型材中，所述型材的静曲强度为45-120MPa，弹性模量为5000-12000Mpa，纤维素和粘性聚合物的质量比为1：(0.1-10.0)。
优选的，上述型材中，所述型材的静曲强度为50-200MPa，弹性模量为6000-15000Mpa；或，纤维素和粘性聚合物的质量比为1：(0.1-10.0)。
优选的，上述型材中，所述型材的静曲强度为100-500MPa，弹性模量为10000-35000Mpa，纤维素和粘性聚合物的质量比为1：(0.1-10.0)。
优选的，上述型材中，所述型材的静曲强度为45-100MPa，弹性模量为5000-12000Mpa，纤维素和粘性聚合物的质量比为1：(0.1-5.0)，特别优选的，纤维素和粘性聚合物的质量比为1：(0.2-4.0)，进一步优选的，纤维素和粘性聚合物的质量比为1：(0.5-3.1)。
优选的，上述型材中，所述型材的静曲强度为50-130MPa，弹性模量为6000-15000Mpa， 纤维素和粘性聚合物的质量比为1：(0.1-7.0)，特别优选的，纤维素和粘性聚合物的质量比为1：(0.6-5.0)，特别优选的，纤维素和粘性聚合物的质量比为1：(0.2-2.0)。
优选的，上述型材中，所述型材的静曲强度为100-500MPa，弹性模量为10000-35000Mpa，优选的，同时型材的拉伸强度为50-300MPa。
优选的，上述型材中，所述型材的静曲强度为200-400MPa，拉伸强度为110-250MPa，弹性模量为13000-30000Mpa，纤维素和粘性聚合物的质量比为1：(0.1-5.0)，尤其优选的，纤维素和粘性聚合物的质量比为1：(0.2-3.0)。
优选的，上述型材中，所述型材的静曲强度、拉伸强度和弹性模量测量时，型材的厚度范围为小于等于3.5mm。
优选的，所述型材中，所述纤维素和所述粘性聚合物均匀分布。即，从纤维素的角度考察，纤维素均匀分布于所述粘性聚合物；反之，从粘性聚合物的角度考察，粘性聚合物均匀分布于所述纤维素。
上述型材通过本发明的实施例证明，其特点是包含纤维素和粘性聚合物，纤维素和粘性聚合物的含量是根据原料的添加量能够明确的，如果原料未知的情况下，通过型材产品也是能够测量得到的。其范围在上述范围内。该型材的静曲强度和弹性模量在一定范围内，从这两个指标看，其性能好于高密度纤维板。
尤其优选的，上述型材中，所述粘性聚合物包含酸不溶木质素，所述酸不溶木质素占型材的质量百分比为1-80％。
优选的，上述型材中，所述粘性聚合物包含酸不溶木质素，所述酸不溶木质素占型材的质量百分比为1-60％，优选的，酸不溶木质素占型材的质量百分比为5-55％，尤其优选的，酸不溶木质素占型材的质量百分比为9.0-53.0％。其中酸不溶木质素包括源自型材制备原料中的酸不溶木质素和外源性酸不溶木质素，其中源自型材制备原料中的木质素占型材的含量百分比为1-28％，所添加的外源性酸不溶木质素占型材的含量百分比为1-25％。
优选的，上述型材中，所述粘性聚合物中除了包含酸不溶木质素外，还包含生物基磺酸钙、聚丙烯(PP)、聚乙烯(PE)、聚氯乙烯(PVC)、聚乳酸(PLA)、聚酰胺(PA)、聚对苯二甲酸乙二酯(PET)、脲醛树脂、酚醛树脂、环氧树脂、大豆蛋白胶、聚酯、聚氨酯、苯丙乳液、异氰酸酯、聚乙烯醇中的一种或多种的粘性聚合物。
优选的，上述型材的制备原料为以纤维素为主的材料和粘性聚合物材料，以纤维素为主的材料和粘性聚合物材料的质量比为1：(0.01-100)。
优选的，上述型材中，以纤维素为主的材料和粘性聚合物材料的质量比为1：(0.1-10)。
优选的，上述型材中，以纤维素为主的材料和粘性聚合物材料的质量比为1：(0.3-2.0)。
优选的，上述型材中，所述粘性聚合物材料为天然粘性聚合物材料和/或合成粘性聚 合物材料中的一种或多种，所述天然粘性聚合物材料为酸不溶木质素或生物基磺酸钙，所述合成粘性聚合物材料选自聚丙烯(PP)、聚乙烯(PE)、聚氯乙烯(PVC)、聚乳酸(PLA)、聚酰胺(PA)、聚对苯二甲酸乙二酯(PET)、脲醛树脂、酚醛树脂、环氧树脂、大豆蛋白胶、聚酯、聚氨酯、苯丙乳液和异氰酸酯中的一种或多种，优选的，所述粘性聚合物材料包含酸不溶木质素，任选地，粘性聚合物材料还包含除酸不溶木质素外的其他粘性聚合物，优选的，所述除酸不溶木质素外的其他粘性聚合物为添加了聚乙烯醇或生物基磺酸钙的聚丙烯、聚乙烯或聚氯乙烯；优选的，粘性聚合物包含以纤维素为主的材料中自带的酸不溶木质素或向以纤维素为主的材料中补加的酸不溶木质素，任选地，粘性聚合物还包含除酸不溶木质素外的其他粘性聚合物，特别优选的，粘性聚合物材料中还包含无机纳米材料。
下文的内容和具体实施方式中，一般也将粘性聚合物材料描述为“粘胶剂”或“胶”，酸化木质素(或称作酸不溶木质素)也作为粘胶剂来使用。
聚乙烯醇和生物基磺酸钙具有增强氢键作用，粘性聚合物中加入聚乙烯醇、生物基磺酸钙等富含羟基的高分子可以通过形成氢键，提高强度和内结合力及耐水性。
优选的，上述型材中，所述生物基磺酸钙为纤维素磺酸钙、半纤维素磺酸钙、淀粉磺酸钙、腐殖酸磺酸钙或甲壳素磺酸钙中的一种或多种。
优选的，所述异氰酸酯为甲苯二异氰酸酯(TDI)、异佛尔酮二异氰酸酯(IPDI)、二苯基甲烷二异氰酸酯(MDI)、二环己基甲烷二异氰酸酯(HMDI)、六亚甲基二异氰酸酯(HDI)或赖氨酸二异氰酸酯(LDI)中的一种或多种。
优选的，上述型材中，所述天然粘性聚合物材料或合成粘性聚合物材料的添加量为型材(例如复合型材或异型材)质量的10-80％，以能够充实纸浆中的骨架单元之间的空隙为最优；优选的，天然粘性聚合物材料或合成粘性聚合物材料的添加量为型材(例如复合型材或异型材)质量的10-50％；优选的，合成粘性聚合物材料为PVC，添加量为型材(例如复合型材或异型材)质量的20-50％，同时添加0.5-5％的聚乙烯醇。
优选的，上述型材中，其特征在于所述以纤维素为主的材料为纸浆、纸产品或植物骨架。
所述植物骨架为保留原植物体如根茎叶果实的基本形状或局部形状，但是其中的细胞结构已经被破坏，细胞中的部分木质素、大部分细胞内化学成分已经流失且保持形状的材料。例如竹块、竹片、竹条、木片、木块、木条、植物秸秆、植物果实外壳等材料，经过酸、碱、或氧化物质处理后，其中的部分木质素被破坏，其中的大部分细胞内成分被去除，但是其依然保留了原始的基本形状，这些材料在本发明中均称为植物骨架。
优选的，上述型材中，所述以纤维素为主的材料为经过机械、物理或化学工艺破坏植物细胞壁，溶出部分木质素及去除可溶性细胞成分，获得保留植物天然骨架结构的材料， 称为植物骨架、或将该植物骨架拆分获得富含纤维素、半纤维素及木质素的本色浆、或由该本色浆进一步加工成的有一定厚度的本色纸作为三大基础原料骨架单元。
优选的，上述型材为通过如下方法制备得到的型材：
将含有纤维素的植物材料经过机械、物理或化学工艺破坏植物细胞壁，溶出部分木质素及去除可溶性细胞成分获得保留天然骨架结构的植物单元材料，或拆分获得富含纤维素、半纤维素及木质素的本色浆，或由该本色浆进一步加工成的有一定厚度的本色纸作为三大基础原料骨架单元，将三大基础原料骨架单元植物单元材料、本色浆、本色纸进行酸化、和/或补加木质素盐(优选木质素钠)后进行酸化，和/或补加酸化回收的酸不溶木质素，和/或添加粘性聚合物材料粉体,和/或添加粘性聚合物薄膜，和/或添加粘性聚合物的溶液，经烘干或成纸，铺装或叠放，热压成型，得到系列新型复合型材或异型材。
优选的，上述以纤维素为主的材料为经物理或化学方法处理的以线性高聚物植物纤维素为主，并富含网状天然生物高分子木质素的多糖材料，该材料中纤维素和木质素分子之间去除了部分木质素分子、部分植物细胞膜成分、部分植物细胞内可水溶成分、可碱溶成分和可酸溶成分，其以纸浆、纸产品或植物骨架的形式存在，这些材料为本发明的以纤维素为主的材料。
优选的，上述型材中，以纤维素为主的材料为纸浆，所述纸浆为富含纤维素、半纤维素及木质素的本色浆；优选的，本色浆是通过酸法或碱法制浆工艺制备得到的本色浆，优选的，本色浆是通过碱法分拆和酸化沉淀有效去除细胞膜和溶解洗出细胞质，具有微米长度，富含纤维素、半纤维素及木质素的自带天然粘性聚合物的本色浆。
优选的，上述型材中，所述纸浆的生产方法包括化学制浆、机械制浆、半机械制浆、生物制浆或废纸回收制浆。优选的，当纸浆的生产方法为非化学制浆的情况下，可在纸浆中添加5-60％的酸不溶木质素或生物基磺酸钙。
优选的，上述型材中，化学制浆为以沉淀木质素的清洁工艺生产本色浆的制浆工艺。
优选的，上述型材中，所述纸浆为植物原料本色浆、漂白浆或回收纸浆。
优选的，上述型材中，植物原料本色浆为含水率为40-70％，pH为9-10，酸不溶木质素含量为1％-50％的竹木本色浆。
优选的，上述型材中，所述植物原料本色浆是通过无黑液制浆工艺制备，通过碱法分拆和酸化沉淀可有效去除细胞膜和溶解洗出细胞质，高收率得到具有一维结构特征微米长度的富含纤维素、半纤维素及木质素的自带天然粘性聚合物酸不溶木质素的本色浆。
其中，植物原料本色浆的制备工艺不但可以大幅减少能耗物耗，而且有效避免了环境污染，最大程度保留了天然木质素的大分子结构，为生物基材料的开发和产业链的延伸提供很好的原创技术和原料基础。
优选的，上述型材中，所述纸浆还包含酸不溶木质素，其中，纤维素和半纤维素的质量之和占纸浆质量比例为50％-90％，所述酸不溶木质素质量占纸浆质量的比例为1-80％。
优选的，上述型材中，所述酸不溶木质素质量占纸浆质量的比例为1-50％。
优选的，上述型材中，所述酸不溶木质素质量占纸浆质量的比例为10-80％。
优选的，上述型材中，所述植物原料本色浆中，酸不溶木质素的质量与纤维素和半纤维素的质量之和的比例为(4-17)：(73-89)，酸不溶木质素、纤维素和半纤维素的质量之和占植物原料本色浆质量百分比为77-99％。
优选的，上述型材中，所述植物原料本色浆的制备方法为：采用质量浓度小于15％的碱在低于130℃下处理植物材料，避免半纤维素和木质素的降解，进一步搓揉磨浆得到纤维素含量为40-80％、半纤维素含量为10-30％和木质素含量为10-80％的本色浆，优选的，所述植物材料为竹、木或植物秸秆。
上述型材中，例如酸不溶木质素、纤维素等占本色浆的质量百分比的计算基础是按照本色浆的干重进行计算。一般情况下，在本发明中，涉及到占比的计算基础，除非有特别说明，一般情况下以干重、固形物重量为基础计算某些成分的重量百分比。
优选的，上述型材中，所述型材的制备方法为：将纸浆和粘性聚合物材料充分混合，然后预压、干燥和热压制备得到型材，优选的，在纸浆中添加酸化木质素或混入合成粘性聚合物材料使其均匀吸附和分散于浆料表面，过滤，烘干后铺装，热压成型得到型材，产品具有阻燃性；优选的，所述酸化木质素为富含木质素盐(优选木质素钠)的黑液，所述合成粘性聚合物材料为合成粘性聚合物粉末或合成粘性聚合物溶液。
优选的，上述型材中，纸浆和粘性聚合物材料的质量比为1：9-9：1，温度的提升，孔隙率的减少，得到的型材强度显著提升，耐水性增加；优选的，在纸浆中添加0.5-5％的聚乙烯醇或生物基磺酸钙。通过添加聚乙烯醇或生物基磺酸钙可弥补结合水损失对材料内结合力的削弱作用。
本发明还提供了上述型材的制备方法，所述方法为：将以纤维素为主的材料和粘性聚合物材料充分混合，然后进行预压、干燥和热压制备得到型材，优选的，所述热压的条件为：温度为100-250℃，压力为1.5-20Mpa，时间为5-60分钟。
研究发现采用低碱量、120℃以下分拆植物原料可以很好避免半纤维素和木质素的降解，通过搓揉磨浆可高得率得到高强度的纤维素、半纤维素和木质素为主要成分的本色浆料，通过补充富含木质素盐(优选木质素钠)的制浆黑液再酸化的简单办法，可使木质素均匀吸附、沉淀分散于浆料表面，方便过滤，这种一维浆骨架原料经烘干后铺装热压成型得到性能优于高密度板的新型材，并具有很好的阻燃性能。因此，在原料过滤或烘干的前期混入树脂或溶液可以很好解决后期的分散难问题，在水分散的浆溶液中加入PVC等合成 塑料的粉末，也可以实现均匀分散，方便过滤，后经烘干后铺装热压成型同样可以得到高性能复合型材，在过滤的纤维表面或气流烘干状态下喷入合成树脂粉末或溶液同样可以达到很好的分散效果。
采用上述原料合成及后处理工艺可以得到性能显著优于人造板及木塑料的新型复合材料，并且可将塑料用量降低到40％以下。
优选的，上述型材的方案中，在于以纤维素为主的材料为纸产品，所述纸产品为富含纤维素、半纤维素及木质素的纸产品，所述纸产品的定量为10-400g/m 2、厚度为0.05-1.00mm，优选的，纸产品为60-150g植物原料来源的纸产品。
目前，还没有以纸基材料作为结构单元通过添加树脂或交替叠放塑料薄膜的加工方式。在本发明中，无论是树脂还是塑料薄膜都是粘性聚合物材料，具有粘结剂性质的粘性聚合物材料。所述纸基材料为纸或纸板，也称为纸产品，优选的，纸产品为纸张、纸屑、纸片、纸粉等。
优选的，上述型材中，纸产品为原浆板、瓦楞面纸、瓦楞芯纸或牛皮纸中的一种或多种；优选的，纸产品为本色浆板或本色浆纸；优选的，纸产品未经表面涂饰，不加填，不施胶；优选的，纸产品为纸浆中补加酸不溶木质素、合成粘性聚合物粉末或合成粘性聚合物的溶液后抄纸、干燥制备得到的纸产品，优选的，所述型材为各向同性，即所述型材的横向静曲强度和纵向静曲强度的相互差异比例小于30％。
优选的，上述型材中，合成粘性聚合物材料添加量为型材质量的10-90％，以填充纸产品和纸产品之间的空隙为最优。尤其优选的，合成粘性聚合物材料添加量为型材质量的10-50％。
优选的，上述型材中，纸产品中酸不溶木质素和纤维素的质量比为(2-19)：(34-68)，酸不溶木质素和纤维素的质量之和占纸产品的质量百分比为77-99％，优选的，酸不溶木质素和纤维素的质量之和占纸产品的质量百分比为75-85％。
优选的，上述型材中，所述纸产品为60-250g/m 2的植物原料来源的纸，或者纸产品为植物原料来源的250-400g/m 2的纸板。
优选的，上述型材中，所述纸产品为纸浆中加入粘性聚合物材料后抄纸成型制备得到纸产品。
优选的，上述型材中，所述型材通过如下制备方法制备得到：利用纸产品即二维生物基材料作为骨架单元，与具有粘胶剂功能的合成粘性聚合物薄膜交错叠放热压成型制备得到型材；或将纸产品喷涂粘性聚合物的溶液或将纸产品浸渍粘性聚合物的溶液，然后烘干得到处理纸产品，然后将处理纸产品叠放或将处理纸产品与纸产品交错叠放，然后热压成型制备得到型材；或在浆料中补加酸化回收的酸不溶木质素，然后抄纸得到处理纸产品， 然后将处理纸产品叠放或将处理纸产品和纸产品交错叠放热压成型制备得到型材；或在浆料中添加合成粘性聚合物颗粒或合成粘性聚合物的溶液，然后抄纸得到处理纸产品，然后将处理纸产品叠放或将处理纸产品和纸产品交错叠放热压成型制备得到型材。
优选的，上述型材中，相邻纸产品顺抄纸流动纹纵横交错，相邻粘性聚合物薄膜顺横向拉伸方向纵横交错，或纸产品与粘性聚合物薄膜相同方向叠加，随着粘性聚合物与木质素流动性的增加，纸基孔隙率的减少，得到的型材强度在主要成分分解温度内随热压温度提高而提升，随含水率的提高而降低，通过表面铺装树脂或热压后表面进行防水处理提高性能。
优选的，上述型材中，所述型材的制备方法是：利用纸产品即二维生物基材料作为骨架单元，与具有粘胶剂功能的粘性聚合物薄膜交错叠放热压成型制备得到型材，粘性聚合物薄膜通过热压与纸产品热压形成铆钉结构，利用物理成键作用粘接成型，其中纸产品的含水率为0.01％-5％。
优选的，上述型材中，粘性聚合物薄膜的厚度为0.02-0.1mm，添加量为型材质量的10-60％；优选的，合成粘性聚合物薄膜为PP薄膜或PV薄膜，合成粘性聚合物薄膜添加量为型材质量的10-50％。
优选的，上述型材中，所述型材的制备方法是：将纸产品喷涂粘性聚合物的溶液或将纸产品浸渍粘性聚合物的溶液，然后烘干得到处理纸产品，然后将处理纸产品叠放或将处理纸产品与纸产品交错叠放，然后热压成型制备得到型材，所述粘性聚合物的溶液的浓度为1-90％wt。
优选的，上述型材中，所述型材的制备方法是：在浆料中补加酸化回收的酸不溶木质素，然后抄纸得到处理纸产品，然后将处理纸产品叠放或将处理纸产品和纸产品交错叠放热压成型制备得到型材，所述酸化回收的酸不溶木质素添加量占浆料干重的1-50％wt。
优选的，上述型材中，通过补加酸化回收的酸不溶木质素对合成粘性聚合物的改性及天然纤维的增强作用，协同物理铆钉结构粘接成型，酸化回收的酸不溶木质素作为多羟基高分子粘性聚合物增强与纤维素之间的氢键作用，减少水量变化对型材強度的影响，同时增强平面内大分子之间及纵向平面之间大分子之间的作用力，使材料强度、韧性和内结合力协同增加。
优选的，上述型材中，所述型材的制备方法是：在浆料中添加粘性聚合物颗粒或粘性聚合物的溶液，然后抄纸得到处理纸产品，然后将处理纸产品叠放或将处理纸产品和纸产品交错叠放热压成型制备得到型材，所述粘性聚合物颗粒的添加量为浆料的质量的百分比为5-150％，优选的，粘性聚合物颗粒的添加量为占浆料的质量的百分比为10-100％，所述粘性聚合物的溶液的浓度为1-99％wt，所述粘性聚合物的溶液中的干物质量占浆料干物质 量的质量百分比为5-50％。
优选的，上述型材中，采用在抄纸过程中混入粘性聚合物粉末或粘性聚合物的溶液，可实现树脂在纸基表面和内部孔隙中的均匀分散，更好地保持纸基内部氢键形成的内结合力，这种以纸基为主的骨架结构可以大大减少树脂用量，降低生产成本，生产高性价比的高强度型材。
优选的，上述型材中，所述型材为各向同性，即所述型材的横向静曲强度和纵向静曲强度的相互差异比例小于等于30％。型材的横向静曲强度和纵向静曲强度的相互差异比例小于等于30％的含义为(横向静曲强度-纵向静曲强度)/横向静曲强度≤30％，或者是(纵向静曲强度-横向静曲强度)/纵向静曲强度≤30％。尤其优选的，所述型材的横向静曲强度和纵向静曲强度的相互差异比例小于等于20％。所述型材的横向静曲强度和纵向静曲强度的相互差异比例小于等于20％的含义为(横向静曲强度-纵向静曲强度)/横向静曲强度≤20％，或者是(纵向静曲强度-横向静曲强度)/纵向静曲强度≤20％。
通过上述方法制备得到的型材，型材各向同性，强度及内结合力大，生产成本低，是具有铆钉结构的新型高强度复合材料型材。
本发明还提供了上述型材的制备方法，所述制备方法为：利用纸产品即二维生物基材料作为骨架单元，与具有粘胶剂功能的合成粘性聚合物薄膜交错叠放热压成型制备得到型材；或将纸产品喷涂粘性聚合物的溶液或将纸产品浸渍粘性聚合物的溶液，然后烘干得到处理纸产品，然后将处理纸产品叠放或将处理纸产品与纸产品交错叠放，然后热压成型制备得到型材；或在浆料中补加酸化回收的酸不溶木质素，然后抄纸得到处理纸产品，然后将处理纸产品叠放或将处理纸产品和纸产品交错叠放热压成型制备得到型材；或在浆料中添加粘性聚合物颗粒或粘性聚合物的溶液，然后抄纸得到处理纸产品，然后将处理纸产品叠放或将处理纸产品和纸产品交错叠放热压成型制备得到型材，其中纸产品和粘性聚合物的质量比为1：(0.1-1.0)，纸产品为富含纤维素、半纤维素及木质素的纸产品；优选的，所述纸产品的定量为10-400g/m 2、厚度为0.05-1.00mm。
优选的，上述型材的制备方法中，所述纸产品的制备浆料为本色浆，所述本色浆为采用低碱量、低温处理植物材料，避免半纤维素和木质素的降解，进一步搓揉磨浆得到含有纤维素、半纤维素和木质素的本色浆。
优选的，上述型材的制备方法中，合成粘性聚合物材料添加量为型材质量的10-90％，以填充纸产品和纸产品之间的空隙为最优。尤其优选的，合成粘性聚合物材料添加量为型材质量的10-50％
优选的，上述型材的制备方法中，所述纸产品为60-250g/m 2的植物原料来源的纸，或者纸产品为植物原料来源的250-400g/m 2的纸板。
优选的，上述型材的制备方法中，所述纸产品为纸浆中加入粘性聚合物材料后抄纸成型制备得到纸产品。
优选的，上述型材的制备方法中，所述纸产品的含水率为0.01％-5％。
优选的，上述型材的制备方法中，粘性聚合物薄膜的厚度为0.02-0.1mm，添加量为型材质量的10-60％；优选的，合成粘性聚合物薄膜为PP薄膜或PV薄膜，粘性聚合物薄膜添加量为型材质量的10-50％。
优选的，上述型材的制备方法中，所述酸化回收的酸不溶木质素添加量占浆料干重的1-50％wt。
优选的，上述型材的制备方法中，所述粘性聚合物颗粒的添加量为浆料的质量百分比为5-150％，所述粘性聚合物的溶液的浓度为1-99％wt，所述粘性聚合物的溶液中的干物质量占浆料干物质量的质量百分比为5-150％，优选的，所述粘性聚合物的溶液中的干物质量占浆料干物质量的质量百分比为10-100％。
优选的，上述型材的制备方法中，所述纸产品通过如下方法制备得到：在清洁制浆工艺过程中或后处理过程中酸化沉淀出酸不溶木质素，或补充酸不溶木质素，或补充粘性聚合物粉末，或补充粘性聚合物的溶液，然后抄纸成型得到纸产品。通过该方法制备的纸产品中，通过纤维束分子内氢键、分子间氢键，与结合水形成的氢键作为内结合力基础，使得所述纸产品成为具有网状结构和一定强度的平面二维纸基材料，该纸产品表面的酸不溶木质素可以增强纸基与树脂的结合力，添加粘性聚合物材料，如聚乙烯醇或生物基磺酸盐，可以减少因为高温结合水缺失导致的内结合力和强度下降，通过浸渍粘性聚合物液体或与粘性聚合物薄膜交错叠合热压可获得具有铆钉结构的高强度新型材。
上述型材利用了纤维素、半纤维素、木质素间羟基的强大氢键使纸产品具有很好的内结合力和力学强度，调节水、聚乙烯醇、生物基磺酸盐等可进一步增强纸产品的内部结合力，以具有较好基础强度。例如，具有互穿网络结构的二维平面牛皮纸作为结构单元，以多层交错叠放的牛皮纸堆作为型材的基本骨架层结构，扩展使用了合成树脂或者成品塑料薄膜等粘性聚合物材料为粘胶剂，通过热压熔融使粘性聚合物材料充分填充纸产品的纤维间空隙，形成具有铆钉结构的高强度新型材。因为纸产品内部和表面具有酸不溶木质素，而酸不溶木质素在纤维表面能够改善与合成材料的界面相容性，增强结合力。
优选的，上述型材的方案中，所述以纤维素为主的材料为植物骨架，所述植物骨架为片状植物材料依次经过碱液处理和酸液处理得到，所述粘性聚合物为植物骨架中保留的天然粘性聚合物材料酸不溶木质素，或者所述粘性聚合物为合成粘性聚合物材料和植物骨架中保留的天然粘性聚合物材料酸不溶木质素。
上述型材是以植物天然骨架为三维结构单元，以天然酸不溶木质素或合成树脂为粘胶 剂的高强度的轻型“竹钢”。
建筑物减重增强和防腐是行业发展的方向，替代大比重钢筋，采用轻型复合材料是建筑材料的发展方向。天然竹子和木材具有较好的强度，由于致密性、强度及结构缺陷无法满足建筑钢筋材料的要求。本发明采取了不破坏植物原料的骨架结构，以充分保留竹/木材料自身力学性能的思路。经过反复实验和摸索终于开发成功了一种基于竹材天然骨架加工成的“竹钢”产品(在发明的下文中称作“型材”)及工艺，竹钢产品的强度可达400MPa，弹性模量可达到33000Mpa。
优选的，上述型材中，所述以纤维素为主的材料为植物骨架，所述植物骨架为片状植物材料依次经过碱液处理和酸液处理得到，所述粘性聚合物为植物骨架中保留的天然粘性聚合物材料酸不溶木质素，或者所述粘性聚合物为合成粘性聚合物材料和植物骨架中保留的天然粘性聚合物材料酸不溶木质素。
优选的，上述型材中，所述型材制备方法为：将片状植物材料依次经过碱液处理和酸液处理得到植物骨架进行热压制备得到型材，优选的，在酸液处理前将碱液处理的片状植物材料浸泡于饱和木质素盐(优选木质素钠)溶液中，所述热压工艺为：根据所选高分子材料，在100℃以上，3-20Mpa热压，时间为15分钟-24小时。
优选的，上述型材中，所述植物骨架为制备方法是：将植物材料处理为平均宽度为1-5cm，按加工要求长度的片材，浸泡到浓度在1％wt以上的NaOH溶液中，在低于130℃下蒸煮1-10h，充分破坏细胞膜溶出木质素及可溶性细胞成分后，得到仍保持片状结构和内部孔道贯通的结构单元，然后，将结构单元重新浸泡到饱和木质素盐(优选木质素钠)溶液中使其尽可能吸附后取出浸泡到稀酸溶液充分酸化或者将结构单元直接浸泡到稀酸溶液充分酸化，然后，再洗涤除去盐及小分子有机物，烘干水分得到植物骨架，优选的，植物材料为竹材、木材或秸秆，优选的，所述竹材为3-5年成年竹去竹青竹黄的竹材。
上述植物骨架的制备方法中，所述植物骨架经过热碱液蒸煮处理和酸化洗涤烘干，得到植物骨架孔隙中保留一定量酸不溶木质素的改性三维片材。
优选的，上述型材中，所述型材的制备方法为：将片状植物材料依次经过碱液处理和酸液处理得到植物骨架，然后添加合成粘性聚合物材料进行热压制备得到型材。优选的，所述热压工艺为：根据所选高分子材料，在100℃以上，3-20Mpa热压，时间为15分钟-24小时。
优选的，上述型材中，所述型材的制备方法中，粘性聚合物材料为具有反应性的异氰酸酯，或添加了聚乙烯醇的聚丙烯、聚乙烯或聚氯乙烯，其中聚乙烯醇具有增强氢键作用。
优选的，上述型材中，所述天然粘性聚合物酸不溶木质素或合成粘性聚合物材料添加量为型材质量的10-70％，以刚好充满骨架单元空隙为最优；优选的，合成粘性聚合物材料 添加量为型材质量的20-50％，优选的，粘性聚合物为合成粘性聚合物材料时，同时加入异型材质量的0.5-5％的聚乙烯醇，有利于提高强度和内结合力。优选的，所述粘性聚合物为天然酸不溶木质素，酚醛树脂，脲醛树脂，PP，PVC，PVA。
优选的，上述型材中，酸不溶木质素和处理后的竹片干重质量比为(1-20)：(70-95)，酸不溶木质素和纤维素的质量之和占型材质量百分比为75-99％。
优选的，上述型材中，所述型材制备方法为：通过热碱溶液蒸煮破坏长尺寸片材的细胞膜，以打通植物细胞间通道，溶出木质素及可溶性细胞成分，得到保持内部空腔和原来形状的竹片材料，再用过量的饱和木质素浸泡溶液使大量木质素进入材料孔隙中，然后取出浸泡好的竹片，再浸入稀酸溶液酸化至内部pH≤4，洗涤除去盐及小分子有机物，然后浸泡于合成粘性聚合物溶液或熔融液中，烘干，可得到保留和更多吸附了天然酸不溶木质素，保留天然骨架结构的三维竹片材料，再单独或堆码，在大于100℃，压力3-20Mpa、时间15分钟-24小时条件下热压，使天然粘性聚合物酸不溶木质素或合成粘性聚合物软化熔融，充满孔隙冷却成型即得到密度大于1，强度超过钢，具有很强耐腐蚀性和阻燃性能的轻型绿色竹钢或竹型材，其拉伸强度可达400MPa，弹性模量可达到33000Mpa，酸不溶木质素含量为10-30％。
本发明还提供了上述型材的制备方法，所述制备方法为：将片状植物材料依次经过碱液处理和酸液处理得到植物骨架进行热压制备得到型材，或者，将片状植物材料依次经过碱液处理和酸液处理得到植物骨架，然后添加合成粘性聚合物材料进行热压制备得到型材，所述热压工艺为：在100℃以上，3-20Mpa热压，时间为15分钟-24小时。
本发明还提供了上述型材的用途，其特征在于所述型材用于用作支撑结构材料、重组竹/木、金属钢材、高密度纤维板、木塑材料或塑料的替代品。
优选的，上述用途中，所述型材外层可再使用阻燃、防水、金属、贴面装饰材料等功能性材料涂覆。
优选的，上述用途中，其特征在于所述型材用于用作高密度纤维板、木塑材料或塑料的替代品。
本发明还提供了上述型材的用途，其特征在于所述型材用于制作支撑结构材料、重组竹/木、金属钢材、高密度纤维板、木塑材料或其它复合材料。
本发明的有益效果
本发明破解了复合纤维材料中纤维素分散难，添加量少，强度不高，弯曲应力大，易变形，各向异性、甲醛污染及阻燃性差等系列难题，达到了显著降低生产成本、大幅提高复合材料的强度和韧性，可以生产强度大大高于塑料、木塑材料等的天然材料的安全环保的高密度纤维板。
与现有技术相比，本发明的有益效果是首创了以牛皮纸等作为二维基础结构单元和骨架材料，利用天然木质素、合成粘性聚合物材料作为粘结材料通过热压生产高强度和高性价比新型材料的简单高效的方法及其产品，实现了以生物基材料为主体的大幅降低树脂或塑料用量的低成本、高性能新型复合材料，其强度、韧性和内结合力都大大超过了天然材料、塑料、塑料纤维复合材料，高密度纤维板，破解了塑料树脂中纤维难分散，添加量少，强度下降幅度大等系列难题。
本发明的型材产品以纸基材料为主要原料，纸基材料采用纸产品，树脂用量合适的情况下，其强度可以达到塑料制品强度的1-15倍。
本发明还开辟了桔杆、竹木等生物质原料高附加值利用的新途径，破解了现有复合材料纤维难分散，无法大量添加，制品强度低、韧性差等难题，原料及性价比优势显著，充分发挥现有的制浆造纸和塑料行业生产平台和产业链优势，可大规模、低成本，连续化清洁生产大尺寸、大用量、安全绿色的板材、型材、管材和异型产品，打造市场潜力巨大的生物基新材料产业链。
本发明利用化学原理和方法破坏植物细胞膜，去除部分木质素和可溶性有机小分子，打通了三维材料组织内部通道，保留竹/木条原外形结构，消除了盐和小分子的干扰，再浸渍饱和的木质素盐(优选木质素钠)溶液或合成树脂溶液或熔融物，可更有效充满三维骨架间隙，减少材料空隙，增加比重，克服了现有重组竹内结合力不足，孔隙难消除、强度难提升的问题，热压成型得到更致密和高强度的复合型材。且产品性能显著优于重组竹，强度超过钢，具有天然耐腐蚀性和阻燃性能的轻型绿色竹钢或竹型材。
上述一维型材(以纸浆作为纤维素为主要成分的原料制备的型材)及制备工艺开辟了桔杆、竹子、木材加工剩余物等生物质高附加值利用新途径，破解了现有各种复合材料中纤维难分散，无法大量添加，制品强度低、韧性差，重组竹弯曲应力大，易变形及各向异性严重等难题，将天然高分子及合成高分子材料拓展为了安全清洁的胶黏剂，开发出了以生物基原料为主，性价比优势显著的新型复合材料系列，可以更好地提升制浆造纸和塑料行业生产平台和产业链优势，可以进行大规模、低成本，连续化清洁生产，并且能够生产出大尺寸、大用量、安全绿色的板材、型材、管材和异型产品，开创了市场潜力巨大的生物基新材料为主导的循环经济产业链。
这一新型材体系的强度和内部结合力显著增加的原因在于非极性高分子粘性聚合物粉体通过热压熔融与纤维单元紧密结合，最大程度填充孔隙，木质素在纤维表面的覆盖可以增加亲油性和纤维材料强度，促进与粘性聚合物间的互溶，纤维晶体、半纤维素及木质素大分子中的多羟基可以相互形成氢键网络，水分子及聚乙烯醇等游离的多羟基大分子有利于增加分子间内结合力，提高型材的强度。
研究发现，随着热压温度增加，合成粘性聚合物及木质素流动性增加，其中的水分或空气进一步逃逸，孔隙率减少，因此，型材强度在粘性聚合物分解温度内随热压温度提高而提升，但含水率过低会降低强度，而添加聚乙烯醇等可以通过增加氢键作用弥补，表面铺装树脂或热压后表面进行防水处理可以进一步提高性能，优选含水率为0.01％-5％。
附图说明
图1是本发明较佳实施例PVC-纤维复合材料的浆骨架基材的立体结构示意图。
图1中各部件的标记为：1、浆纤维；2、树脂材料
图2是PVC-纤维基复合材料实物图。
图3是本发明树脂-纤维基复合材料的力学强度性能图。
图4是本发明较佳实施例树脂-纸基复合材料的纸骨架基材立体结构示意图。
图4中各部件的标记为：A、牛皮纸；2、树脂薄膜
图5-A是本发明树脂-纸基复合材料的力学强度性能图。
图5-B是纯树脂与本发明树脂-纸基复合材料的力学强度性能对比图。
图5-C是本发明树脂-纸基复合材料的内结合强度与24小时吸水厚度膨胀率图。
图6-A是市售80g/m 2牛皮纸电镜图。
图6-B是市售80g/m 2牛皮纸为原料，20％PP添加量的PP-纸基复合材料电镜图。
图7-A是70g/m 2牛皮纸电镜图。
图7-B是70g/m 2牛皮纸为原料，38％PP添加量的PP-纸基复合材料电镜图。
图8-A是70g/m 2牛皮纸电镜图，与图7-A相同，为强化对比重复放置此图。
图8-B是70g/m 2牛皮纸为原料，28％PVC添加量的PVC-纸基复合材料电镜图。
图8-C是70g/m 2牛皮纸为原料，33％PVC添加量的PVC-纸基复合材料电镜图。
图8-D是70g/m 2牛皮纸为原料，45％PVC添加量的PVC-纸基复合材料电镜图。
图9-A是PP-纸基复合材料力学强度与PP添加量比例，热压温度的关系图。
图9-B是PVC-纸基复合材料力学强度与PVC添加量比例，热压温度的关系图。
图9-C是PA-纸基复合材料力学强度与PA添加量比例，热压温度的关系图。
图9-D是PA-纸基复合材料力学强度与纸基类型的关系图。
图10-A是原竹纵面电镜图。
图10-B是竹钢纵面电镜图(放大150倍)，显示纤维束与薄壁细胞均被致密压缩。
图10-C是竹钢纵面电镜图(放大700倍)，显示线状纤维束排列整齐，非常致密。
图10-D是竹钢纵面电镜图(放大800倍)，显示纤维束非常致密。
图11本发明竹钢力学性能与木质素含量关系图。图中8.1％/PVA指复合材料中添加了 木质素及PVA，其中木质素的添加比例为8.1％，PVA的添加比例为2％。
具体实施方式
下面结合附图对本发明的较佳实施例进行详细阐述，以使本发明的优点和特征能更易于被本领域技术人员理解。需要说明的是，本实施例是描述性的，不是限定性的，不能由此限定本发明的保护范围。
下述实施例中所制备的型材在测量性能过程中，所述型材的厚度范围为3.5mm以内。
实施例1：
1、竹片用浓度为13％的NaOH溶液75℃煮10-12h，经过搓柔磨浆得到含水率60％，pH为9-10的绿本色竹浆，用2％的稀硫酸酸化至pH为2-3，清水洗涤干净，筛浆，经纤维疏解器疏解，配制浆浓度为1％的料液备用。测量酸化后本色竹浆(以干重计)中的纤维素(含半纤维素)的质量含量为58.98％，酸不溶木质素的含量为23.96％。
2、按比例添加粒径＜300目的PVC粒料或PLA粒料混合均匀，置于50cm*50cm自制预压系统(M＝30Kg)自然预压20min，得到厚度15±1mm的浆骨架基材，在＜100℃干燥，PVC-纤维复合材料的浆骨架基材的立体结构示意图参见附图1，实物参见附图2。
可以看出：PVC添加量仅为31.01％，热压条件为185℃，10MPa，热压10min的PVC-纸浆复合材料的静曲强度为62.15MPa、弹性模量为5235MPa，24h吸水厚度膨胀率为8.10％，结果均优于GB/T 31765-2015中所述的高湿型高密度纤维板静曲强度(42.0MPa)、弹性模量(3800MPa)，24h吸水厚度膨胀率(12.0％)的要求。
表1 PLA-本色浆材料的制备条件及产品性能
Figure PCTCN2021080480-appb-000001
表1的结果表明：在型材中，PLA的添加量为15％左右，PLA和酸不溶木质素的质量之和与纤维素的质量比约为0.72(纤维素和粘性聚合物的质量比为1.39)的情况下，静曲强度为57MPa，弹性模量为7100MPa，结果均优于GB/T 31765-2015中所述的高湿型高密度纤维板静曲强度(42.0MPa)、弹性模量(3800MPa)的要求。
表2 PVC-本色浆料的制备条件及产品性能
Figure PCTCN2021080480-appb-000002
Figure PCTCN2021080480-appb-000003
表2的结果表面：在PVC添加量为30-60％左右，粘性聚合物PVC和酸不溶木质的质量之和与纤维素的质量比约为1.14-3.05(纤维素和粘性聚合物的质量比为0.33-0.88)的情况下，热压条件为180-185℃，5-10MPa，热压9-15min的PVC-纸浆复合材料的静曲强度为最高达到62.15MPa，最低达到43.41MPa，弹性模量最高为5235MPa，最低为3994MPa，结果均优于GB/T 31765-2015中所述的高湿型高密度纤维板静曲强度(42.0MPa)、弹性模量(3800MPa)的要求，对于序号为3、4、5、6、7、9的24h吸水厚度膨胀率满足GB/T 31765-2015中所要求24h吸水厚度膨胀率(12.0％)的要求，甚至24h吸水厚度膨胀率最低可达到1.91％的指标。
实施例2：
1、制浆方法同上述实施例1的步骤1。
2、按比例加入粒径大于1微米的CaCO 3或/和CaSO 4粉体混合均匀，预压方法同上述实施例1的步骤2。
3、按比例添加PVA溶液，＜100℃干燥；
4、浆骨架基材经热压，保压冷却得到产品，具体热压条件及型材性能见表3。
表3 PVA-本色浆料的制备条件及产品性能
Figure PCTCN2021080480-appb-000004
表3的结果表明：添加量在15％以下的PVA-纤维基复合材料，不加入纳米钙剂材料的情况下，粘性聚合物PVA和酸不溶木质素的质量之和与纤维素的质量比为0.69(纤维素和粘性聚合物的质量比为1.45)的情况下，其静曲强度和弹性模量均远优于GB/T 31765-2015中所描述的普通高密度纤维板静曲强度(38.0MPa)、弹性模量(3900MPa)的要求。
PVA添加量在15％以下的PVA-纤维基复合材料，粘性聚合物PVA和酸不溶木质素的质量之和与纤维素的质量比为0.85左右(纤维素和粘性聚合物的质量比为1.18左右)的情况下，即使再加入10％的纳米钙基材料，其静曲强度和弹性模量均远优于GB/T 31765-2015中所描述的普通高密度纤维板静曲强度(38.0MPa)、弹性模量(3900MPa)的要求。
实施例3：
1、用13％的NaOH溶液在75℃下煮竹片10-12h，经过搓柔磨浆得到含水率60％，pH为9-10的本色竹浆，测量木本色浆(以干重计)中的纤维素(含半纤维素)的质量含量为83.07％，酸不溶木质素的含量为6.02％，补充副产木质素钠溶液，按照表4比例混合均匀，用2％的稀硫酸酸化至pH为2-3。
2、按配比在料液中加入一定比例的浓度为2％的聚乙烯醇，经热压，保压冷却得到产品，具体性能见表4。
表4 本色浆材料的制备条件及产品性能
Figure PCTCN2021080480-appb-000005
表4的结果表明：木质素、PVA、苯丙乳液及本色浆中含有的酸不溶木质素一起作为粘性聚合物，使得粘性聚合物与纤维素的质量比例为0.77-1.46(纤维素和粘性聚合物的质量比为0.69-1.30)，含有本色竹浆和作为木质素为主的粘结剂的热压产品的静曲强度和弹性模量远优于普通高密度纤维板静曲强度(38.0MPa)、弹性模量(3900MPa)的要求，且无法点燃，具有优异的阻燃性能。添加极性的PVA可进一步提升性能。
实施例4：
1、用13％的NaOH溶液在75℃下煮3-5年竹片10-12h，经过搓柔磨浆得到含水率60％，pH为9-10的本色竹浆，2％的稀硫酸酸化至pH为2-3，清水洗涤干净，筛浆，取50g的本色浆，添加固含量50％的苯丙乳液，以及按竹纤维浆的质量比例添加固含量50％的纤维素磺酸钙溶液，混合均匀烘干，得到型材原料混合物。其中本色竹浆中的纤维素和酸不溶木质素含量同实施例1，苯丙乳液添加量和纤维素磺酸钙添加量均以固含量计算。
2、将型材原料混合经热压，保压冷却得到产品，具体工艺及性能见表5。
表5 本色浆材料的制备条件及产品性能
Figure PCTCN2021080480-appb-000006
表5中，乳液的百分比含量为本色浆的百分比含量，纤维素磺酸钙为型材原材料干物质总质量的百分比含量，通过计算，通过表5制备的型材中，粘性聚合物中乳液、纤维素磺酸钙和本色浆中的酸不溶木质素的总质量与纤维素的质量比为0.59-1.25(纤维素和粘性聚合物的质量比为0.80-1.71)。也就是当产品添加苯丙乳液后再添加纤维素磺酸钙之后，使得型材中的纤维素和粘性聚合物的质量比例在0.80-1.71的情况下，材料的静曲强度和弹性模量远优于普通高密度纤维板静曲强度(38.0MPa)、弹性模量(3900MPa)的要求。
以上实施例以纸浆作为微纳米纤维原料，以酸化析出的木质素或合成树脂作为粘接剂，经热压成型生产出静曲强度为45-120MPa的各类新型复合型材，均优于国标潮湿型高密度 纤维板静曲强度(42.0MPa)、弹性模量(3900MPa)的要求，参见附图3。
实施例5：
1、经选市售80(厚度0.1mm)g/m 2牛皮纸(以下相同克数牛皮纸原料相同，无填料，重施胶，其中纤维素含量为76.24％，酸不溶木质素含量5.76％)剪裁成一定规格的纸片1，选择塑料薄膜(0.01-0.1mm)剪裁成与纸片1相同规格的胶片2，＜100℃干燥备用。
2、取26张纸片1与25张胶片2交替横纵交错叠加得到树脂-纸基复合材料的纸骨架基材。树脂-纸基复合材料的纸骨架基材立体结构示意图见附图4，性能参见附图5-A、附图5-B和附图5-C。
3、将纸骨架基材经热压，保压冷却得到产品。
4、80g/m 2牛皮纸电镜图和20％PP添加量的PP-纸基复合材料电镜图参见附图6-A和附图6-B。
5、各种条件下制备的型材性能见表6。
表6 牛皮纸为原料的PP-纸基复合材料的制备条件及产品性能
Figure PCTCN2021080480-appb-000007
可见，在纸基质量为50-90％，PP塑料含量为10-50％的情况下，也就是PP塑料和牛皮纸中的酸不溶木质素的质量之和(粘性聚合物总质量)与牛皮纸中的纤维素的质量比为 0.22-1.39(纤维素和粘性聚合物的质量比0.72-4.52)，通过热压时间为15-20分钟，热压温度为175-195℃，压力5-8MPa的条件制备的型材，其静曲强度可以达到45-92MPa，弹性模量可以达到4000-13237MPa。例如，表6中序号15的型材，PP添加量为20％，热压条件为190℃，8MPa，热压15min的PP-纸基复合材料的静曲强度为92.52MPa、弹性模量为13124MPa，远优于普通高密度纤维板静曲强度(38.0MPa)、弹性模量(3900MPa)的要求。
复合材料不同含水率的产品性能差异较大，具体情况参见如下表7。
表7 80g/m 2市售牛皮纸为原料，PP添加率为20％的复合材料不同含水率情况下的产品性能
Figure PCTCN2021080480-appb-000008
制备型材过程中，控制型材(即复合材料)的含水率低于5％的情况下，型材能够保持型材的静曲强度和弹性模量，当然，含水率提高的情况下，材料的静曲强度和弹性模量均会降低。
实施例6：
1、经选70g/m 2(厚度0.08mm)自制不施胶，不加填的牛皮纸(以下相同克数牛皮纸原料相同，其中纤维素含量为58.98％，酸不溶木质素含量为23.96％)剪裁成一定规格的纸片1备用，选择市售PP塑料薄膜(0.01-0.1mm)剪裁成与纸片1相同规格的胶片2，＜100℃干燥备用，选择市售PVA，聚合度1700-1800，分子量84000-89000，配置3％的溶液，取胶片2定量浸润PVA溶液，＜70℃烘干得到胶片3备用。
2、取26张纸片1，与25张胶片2或胶片3交替横纵交错叠加得到树脂-纸基复合材料的纸骨架基材。
3、纸骨架基材经热压，保压冷却得到产品，各种条件下的产品性能见表8-10。
4、70g/m 2牛皮纸电镜图和38％PP添加量的PP-纸基复合材料电镜图参见附图7-A和附图7-B。
5、PP-纸基复合材料力学强度与PP添加量比例，热压温度的关系参加图9-A。
表8 70g/m 2自制牛皮纸为原料的PP-纸基材料制备条件及产品性能
Figure PCTCN2021080480-appb-000009
Figure PCTCN2021080480-appb-000010
PP添加量为22.10％，PP和牛皮纸中的酸不溶木质素的质量之和(粘性聚合物总质量)与牛皮纸中的纤维素的质量比为0.89(纤维素和粘性聚合物的质量比为1.13，其中PP为粘性聚合物，牛皮纸中的酸不溶木质素也为粘性聚合物)，通过热压条件为热压7MPa，热压15min，热压温度从180-210℃，制备得到PP-纸基复合材料强度随温度变化不大，优于潮湿型高密度纤维板静曲强度(42.0MPa)、弹性模量(3900MPa)的要求。
表9 70g/m 2自制牛皮纸为原料，不同PP添加量的PP-纸基材料制备条件及产品性能
Figure PCTCN2021080480-appb-000011
改变粘性聚合物和纤维素的比例，表9中，粘性聚合物(PP和牛皮纸中的酸不溶木质素质量之和)和牛皮纸中的纤维素的质量比为0.87-1.20(纤维素和粘性聚合物的质量比例为0.83-1.15)的情况下，随着PP添加量的提高，PP流动性增强，更容易填充于三维纤维的空隙间，材料强度提升。热压条件为7MPa，210℃热压15分钟，当PP添加量大于27.98％时，材料性能远优于潮湿型高密度纤维板静曲强度(42.0MPa)、弹性模量(3900MPa)，内结合力(1.20MPa)，吸水厚度膨胀率(16.0％)的要求。
牛皮纸与PP树脂交错叠合热压成型后形成的材料横切面看不出牛皮纸原本的非均质网状结构，PP被均匀填充于牛皮纸之间的空隙，与牛皮纸之间形成类似铆钉结构，使PP于纤维更好的相互作用，因此复合材料具有优异的力学性能。具体参见附图9-A。
表10 70g/m 2自制牛皮纸为原料的PP/PVA-纸基材料制备条件及产品性能
Figure PCTCN2021080480-appb-000012
表10中，合成粘性聚合物为PP和PVA，PP和PVA作为合成粘性聚合物，牛皮纸中的 酸不溶木质素作为天然粘性聚合物，粘性聚合物的质量之和(PP+PVA+酸不溶木质素)与牛皮纸中的纤维素质量比例分别为0.89、1.00、1.15(纤维素和粘性聚合物的质量比为1.13、1.00、0.87)，所制备得到型材均优于潮湿型高密度纤维板静曲强度(42.0MPa)、弹性模量(3900MPa)的要求。而且，随着PVA的添加，增加了氢键作用，强度提升显著。添加9.04％的PVA后，静曲强度增加43.88％，弹性模量，内结合力提升显著。
实施例7：
1、将牛皮纸(与实施例6中采用的牛皮纸相同)剪裁成一定规格的纸片1，选择市售PVC塑料薄膜(0.01-0.1mm)剪裁成与纸片1相同规格的胶片2，＜100℃干燥备用。
2、将纸片1与胶片2纵横交替叠加25张得到树脂-纸基复合材料的纸骨架基材。
3、纸骨架基材经热压，保压冷却得到产品，各种条件得到的材料的性能见表11。
4、70g/m 2牛皮纸电镜图和不同PVC添加量的PVC-纸基复合材料电镜图参见附图8-A、附图8-B、附图8-C和附图8-D。
5、PVC-纸基复合材料力学强度与PVC添加量比例，热压温度的关系参见附图9-B。
表11 70g/m 2自制牛皮纸为原料的PVC-纸基材料制备条件及产品性能
Figure PCTCN2021080480-appb-000013
从表11可以看出，采用70g/m 2本色纸为原料，当PVC添加量为40％左右(纤维素和粘性聚合物的质量比为0.63-0.65)，热压条件为6MPa，热压15min，随着热压温度从175-195℃的提升，制备得到PVC-纸基复合材料静曲强度提升，190℃之后木质素活性增强，对PVC改性作用增强，材料静曲强度显著提升，195℃时拉伸强度为71.76MPa，静曲强度为120.38MPa、弹性模量为8250.80MPa，24h吸水厚度膨胀率为13.97％，远优于潮湿型高密度纤维板静曲强度(42.0MPa)、弹性模量(3900MPa)要求，是UPVC拉伸强度(29.4MPa)的2.4倍，静曲强度(45.6MPa)的2.64倍，是硬质PVC弹性模量(1500-3000MPa)的2.75倍。而且序号为1、4、5所制备得到的型材还满足24h吸水厚度膨胀率(16.0％)的要求。
实施例8：
1、经选80g/m 2(厚度0.1mm)牛皮纸(其中纤维素含量为76.24％，酸不溶木质素含量5.76％)剪裁成一定规格的纸片1，选择高密度聚乙烯HDPE薄膜(0.01-0.1mm)剪裁成 与纸片1相同规格的胶片2，＜100℃干燥备用，选择PLA薄膜(0.01-0.1mm)剪裁成与1相同规格的胶片3，＜100℃干燥备用。
2、将纸片1与胶片2纵横交替叠加25张得到HDPE-纸基复合材料的纸骨架基材，将单片1与胶片3纵横交替叠加25张得到PLA-纸基复合材料的纸骨架基材。
3、HDPE-纸基复合材料的纸骨架基材和PLA-纸基复合材料的纸骨架基材经热压，保压冷却得到产品，具体性能见表12、13。
表12 HDPE-纸基材料的制备条件及产品性能
Figure PCTCN2021080480-appb-000014
表13 PLA-纸基材料的制备条件及产品性能
Figure PCTCN2021080480-appb-000015
表12中的HDPE-纸基复合材料(纤维素与粘性聚合物质量比为2.03)及表13中的PLA-纸基复合材料(纤维素与粘性聚合物质量比为0.77)静曲强度和弹性模量性能均优于普通高密度纤维板静曲强度(38.0MPa)、弹性模量(3900MPa)的要求。采用相邻纸基纵横交错的加工方式制备得到的HDPE-纸基复合材料各向同性，横纵方向的静曲强度和弹性模量性能均优于普通高密度纤维板静曲强度(38.0MPa)、弹性模量(3900MPa)的要求。
实施例9：
1、经选市售80g牛皮纸(与实施例8所用牛皮纸相同)剪裁成一定规格的纸片1。
2、选择固含量为50％的苯丙乳液，调节pH至4-6。
3、采用单张滚胶方式，控制施胶(苯丙乳液)量1：1，＜100℃干燥至单张含水率＜10％，且纸片含有胶膜，将纸片纵横交错叠加50张。
4、纸骨架基材经热压，保压冷却得到产品，具体性能见表14。
表14 苯丙乳液-纸基材料的制备条件及产品性能
Figure PCTCN2021080480-appb-000016
表14的结果表明，苯丙乳液-纸基复合材料(纤维素与粘性聚合物质量比为1.33)的静曲强度和弹性模量均优于潮湿型高密度纤维板静曲强度(38.0MPa)、弹性模量(3900MPa)、70℃静曲强度(15.0MPa)的要求。
实施例10：
1、经选80g牛皮纸(与实施例8所用牛皮纸相同)剪裁成一定规格的纸片1。
2、选择固含量为20％的脲醛胶，质量分数为20％的MDI溶液。
3、采用喷涂方式，控制施胶比例，纸片1纵横交错叠加50张。
4、纸骨架基材经热压，保压冷却得到产品脲醛-纸基复合材料、MDI-纸基复合材料具体性能见表15。
表15 纸基材料的制备条件及产品性能
Figure PCTCN2021080480-appb-000017
表15中，纤维素与粘性聚合物质量比为4.52，表明，具有反应性的MDI在较低的添加量情况下，能够使得型材具有有较高的静曲强度和内结合强度，可作为复合组份。
实施例11：
1、经选70g/m 2牛皮纸剪裁成一定规格的纸片1，选择市售PA塑料薄膜(0.01-0.1mm)剪裁成与1相同规格的胶片2，＜100℃干燥备用。
2、将纸片1与胶片2纵横交替叠加25张得到PA-纸基复合材料的纸骨架基材。
3、纸骨架基材经热压，保压冷却得到产品，具体性能见表16。
4、PA-纸基复合材料力学强度与PVC添加量比例，热压温度的关系图参见附图9-C。
表16 PA-纸基材料的制备条件及产品性能
Figure PCTCN2021080480-appb-000018
Figure PCTCN2021080480-appb-000019
从表16可看出，当PA添加量为28％(纤维素和粘性聚合物的质量比为0.94)，热压条件为6MPa，热压10min，随着热压温度从225-245℃的提升，制备得到PA-纸基复合材料的静曲强度先提升后降低，温度升高，木质素活性增强，对PA改性作用增强，材料静曲强度显著提升，超过235℃，因纸基中半纤维素和木质素分解作用，各项性能下降。235℃时静曲强度为135.12MPa、弹性模量为9608MPa，24h吸水厚度膨胀率为14.63％，强度远优于潮湿型高密度纤维板静曲强度(42.0MPa)、弹性模量(3900MPa)要求，24h吸水厚度膨胀率(16.0％)也达到要求。
PP/PVC/PA-纸基复合材料力学强度与树脂添加量比例，热压温度的关系图参见表9-A/B/C，PA-纸基复合材料力学强度与纸基克数的关系图参见附图9-D。从图中可看出，热压温度升高，树脂流动性增强，复合材料性能提升；一定温度后，性能变化不大，温度过高，性能不稳定，跟树脂分解有关。随着树脂添加率升高，力学性能提升；同时，由于纤维与树脂不相容，树脂添加率过高便会溢出；纸基厚度或过薄，力学性能降低。且强极性的PVC与PA的复合材料性能优于非极性树脂PP复合材料，纤维素是亲水性的高分子，能与PVC和PA发生作用的是极性材料木质素，因而含有木质素的纤维素纸基作为基体材料利用简单的加工方式强化了每种原料的优势，树脂添加率30％远优于同等材料，成本低，解决了现在竹塑木塑材料无法大比例添加纤维的难题。
实施例12：
1、分别经选毛竹片20片，100mm*6mm*4mm，置于2.5L的2.5mol/L的NaOH及0.4mol/L的Na 2SO 3混合溶液中煮沸，蒸煮条件参见如下表17，洗去浮碱，分别浸入pH＝3的硝酸、稀硫酸，硫酸铝溶液中浸泡0.5h。酸化过后的竹片置于洗去浮酸，自然晾干备用。
2、将竹片经100℃，5MPa热压24h，自然冷却，室温放置36h后进行力学性能测定，如表17。
表17 高强度重组纤维材料的制备条件及产品性能表
Figure PCTCN2021080480-appb-000020
Figure PCTCN2021080480-appb-000021
表17的型材中，空白为处理的竹片的拉伸强度和弹性模量性能，将其碱水解后酸化，形成含有酸不溶木质素的三维竹材料(纤维素含量和酸不溶木质素含量比为2.5-14.9)，经热压可得到拉伸强度接近400MPa强度超过钢铁Q235的竹钢。
实施例13：
1、经选工厂毛竹条，＜150℃烘干，宽19.0±0.5mm，厚4.36±0.02mm；密度：0.75±0.02g/cm 3。
2、取毛竹条25根，置于2.5MNaOH溶液中煮沸加热2h，然后浸入到3.6％的稀硫酸中2-4h(20ml浓硫酸加入1L水)。
3、酸化过后的竹条置于沸腾的水中清洗干净，自然晾干至含水率为30％备用。
4、浸泡于28％的酚醛溶液达到所需的浸胶量，85℃烘干至含水率＜10％。
5、将烘干后的竹条整齐单层排列成150mm*200mm规格置于模具中，按照设定的压力温度径向压缩，自然冷却，室温放置36h后进行力学性能测定，如表18。
6、致密材料的电镜图如附图10-A、10-B、10-C和10-D。
表18 高强度重组纤维材料的制备条件及产品性能表
Figure PCTCN2021080480-appb-000022
Figure PCTCN2021080480-appb-000023
表18中，空白为未处理竹条直接测量静曲强度和弹性模量的性能，序号为1号的是经过碱水解后酸化且未添加胶的竹条经过热压得到的型材的静曲强度和弹性模量的性能。2-4号为添加酚醛后所制备得到型材(纤维素含量和粘性聚合物含量比为1.3-1.7)，其冲击韧性相对于原竹条均有提高。根据重组竹文献，弹性模量18000MPa时，静曲强度达到160MPa，则为优等品，4号产品静曲强度为188.94MPa，是重组竹优等品1.18倍。
实施例14：
1、经选工厂毛竹条，＜150℃烘干，宽19.0±0.5mm，厚4.36±0.02mm；密度：0.75±0.02g/cm 3。
2、取毛竹条25根，置于2.5MNaOH溶液中分别煮沸加热2h和4h，浸入饱和木质素钠溶液24h，洗去浮碱，再浸入3.6％的稀硫酸中2-4h(20ml浓硫酸加入1L水)。
3、酸化过后的竹条置于沸腾的水中清洗干净，自然晾干备用。
4、将烘干后的竹条单层排列成150mm*200mm规格置于模具中，按照设定的压力温度径向压缩，自然冷却，室温放置36h后进行力学性能测定，如表19。
表19 高强度重组纤维材料的制备条件及产品性能表
原料处理 胶 热压条件 厚度/mm 静曲强度/MPa
未处理 —— —— 4.36 143
煮2h 木质素 5MPa，180℃，15min 1.94 160.99
煮4h 木质素 5MPa，180℃，15min 2.99 194.93
表19中，通过添加木质素钠后进行酸化，提高酸不溶木质素含量(纤维素含量和酸不溶木质素含量比为2.0-4.2)，天然竹条的静曲强度为143Mpa，在碱煮2h和4h后，通过添加木质素钠和酸化，补充酸不溶木质素，使得材料的静曲强度是天然竹条(未处理)的1.13倍和1.36倍。
实施例15：
1、经选工厂毛竹条，＜150℃烘干，宽19.0±0.5mm，厚4.36±0.02mm；密度：0.75±0.02g/cm 3。
2、分别取竹片25根，置于2.5M的NaOH溶液中煮沸加热2h，5h，9h，洗去浮碱，浸入3.6％的稀硫酸溶液中至最终pH为中性，热水煮沸15min。
3、取竹片25根，置于2.5M NaOH溶液中煮沸加热5h，捞出置于煮沸的饱和木质素钠溶液1h，洗去浮碱，浸入3.6％的稀硫酸溶液中至最终pH为中性，热水煮沸15min后置于 5％的PVA溶液中浸泡30min。
4、分别将将步骤2和步骤3的竹片180℃烘干20min，单层排列成150mm*200mm规格置于模具中，230℃，7MPa径向压缩30min，自然冷却，室温放置36h后进行力学性能测定(纤维素含量和粘性聚合物比为2.2-10.5)，结果参见附图11。可以看出，该方法制得的材料静曲强度(图中标为弯曲强度)为199-306MPa，弹性模量均大于18GPa(即18000MPa)，冲击韧性为12.06-15.30KJ/m 2，当木质素含量为12.5％时(步骤2中NaOH溶液中煮沸加热5h)，型材(竹钢)弯曲强度达到306.03MPa。当添加2％的PVA(步骤3中5％的PVA溶液中浸泡30min后型材中PVA含量为2％)，弯曲性能增加到393.68MPa，冲击韧性提高到61.9KJ/m 2，说明PVA的添加增强了分子内和分子间的氢键作用，显著提升了材料的强度与韧性。
实施例16：
1、经选工厂毛竹条，长度2100.0mm；宽度25.0mm；厚度3.0mm。置于5％的NaOH溶液中95℃蒸煮3h，烘至含水率＜10％。
2、经步骤1处理的毛竹条按照重组竹常规工艺处理，施泰尔胶10％，<50℃干燥3-4h，含水率<10％，取处理过后的竹束85kg顺纤维方向装模，在140-145℃，6MPa，30min条件下热压成型。
3、经裁边得到的产品(纤维素含量和粘性聚合物含量比为1.6)规格为：长1850mm，宽140mm，厚18mm，按照GB/T 17657-2013方法测定，产品密度为1.33g/cm 3，静曲强度161MPa(深炭板≧70MPa)，弹性模量15739MPa，吸水厚度膨胀率4％。通过本发明创造的产品的密度，力学及防水等主要性能均满足国标GB/T30364中的要求，静曲强度是国标的2.3倍。
需要强调的是，本发明所述的实施例是说明性的，而不是限定性的，因此本发明并不限于实施方式中所示的实施例，凡是利用本发明说明书及附图内容所作的等效结构或等效流程变换，或直接或间接运用在其他相关的技术领域，均同理包括在本发明的专利保护范围内。

Claims (21)

  1. 一种新型复合型材，其特征在于所述型材包含纤维素和粘性聚合物，所述型材的静曲强度为40-500MPa，弹性模量为4000-40000Mpa，纤维素和粘性聚合物的质量比为1：(0.01-100)。
  2. 根据权利要求1所述的型材，其特征在于所述型材的静曲强度为45-120MPa，弹性模量为5000-12000Mpa，纤维素和粘性聚合物的质量比为1：(0.1-10.0)；或，型材的静曲强度为50-200MPa，弹性模量为6000-15000Mpa，纤维素和粘性聚合物的质量比为1：(0.1-10.0)；或，型材的静曲强度为100-500MPa，弹性模量为10000-35000Mpa，纤维素和粘性聚合物的质量比为1：(0.1-10.0)。
  3. 根据权利要求1所述的型材，其特征在于所述粘性聚合物包含酸不溶木质素，所述酸不溶木质素占型材的质量百分比为1-80％。
  4. 根据权利要求1所述的型材，其特征在于所述型材的制备原料为以纤维素为主的材料和粘性聚合物材料，以纤维素为主的材料和粘性聚合物材料的质量比为1：(0.01-100)。
  5. 根据权利要求4所述的型材，其特征在于所述粘性聚合物材料为天然粘性聚合物材料和/或合成粘性聚合物材料中的一种或多种，所述天然粘性聚合物材料为酸不溶木质素或生物基磺酸钙，所述合成粘性聚合物材料选自聚丙烯、聚乙烯、聚氯乙烯、聚乳酸、聚酰胺、聚对苯二甲酸乙二酯、脲醛树脂、酚醛树脂、环氧树脂、大豆蛋白胶、聚酯、聚氨酯、苯丙乳液和异氰酸酯中的一种或多种；优选的，所述粘性聚合物材料包含酸不溶木质素，任选地，粘性聚合物材料还包含除酸不溶木质素外的其他粘性聚合物；优选的，所述除酸不溶木质素外的其他粘性聚合物为添加了聚乙烯醇或生物基磺酸钙的聚丙烯、聚乙烯或聚氯乙烯；优选的，粘性聚合物材料包含以纤维素为主的材料中自带的酸不溶木质素或向以纤维素为主的材料中补加的酸不溶木质素，任选地，粘性聚合物材料还包含除酸不溶木质素外的其他粘性聚合物，特别优选的，粘性聚合物材料中还包含无机纳米材料。
  6. 根据权利要求5所述的型材，其特征在于所述以纤维素为主的材料为纸浆、纸产品或植物骨架。
  7. 根据权利要求6所述的型材，其特征在于以纤维素为主的材料为纸浆，所述纸浆为富含纤维素、半纤维素及木质素的本色浆；优选的，本色浆是通过酸法或碱法制浆工艺制备得到的本色浆，优选的，本色浆是通过碱法分拆和酸化沉淀有效去除细胞膜和溶解洗出细胞质，具有微米长度，富含纤维素、半纤维素及木质素的自带天然粘性聚合物的本色浆。
  8. 根据权利要求7所述的型材，其特征在于所述纸浆还包含酸不溶木质素，其中， 纤维素和半纤维素的质量之和占纸浆质量比例为50％-90％，所述酸不溶木质素质量占纸浆质量的比例为1-50％。
  9. 根据权利要求7所述的型材，其特征在于所述植物原料本色浆的制备方法为：采用质量浓度小于15％的碱在低于130℃下处理植物材料，避免半纤维素和木质素的降解，进一步搓揉磨浆得到纤维素含量为40-80％、半纤维素含量为10-30％和木质素含量为10-80％的本色浆，优选的，所述植物材料为竹、木或植物秸秆。
  10. 根据权利要求7-9任一项所述的型材，其特征在于所述型材的制备方法为：将纸浆和粘性聚合物材料充分混合，然后预压、干燥和热压制备得到型材，优选的，在纸浆中添加酸化木质素或混入合成粘性聚合物材料使其均匀吸附和分散于浆料表面，过滤，烘干后铺装，热压成型得到型材，产品具有阻燃性；优选的，所述酸化木质素为从富含木质素盐的制浆黑液中酸化得到，所述合成粘性聚合物材料为合成粘性聚合物粉末或合成粘性聚合物溶液。
  11. 权利要求7-9任一项所述型材的制备方法，所述制备方法为：将以纤维素为主的材料和粘性聚合物材料充分混合，然后进行预压、干燥和热压制备得到型材，优选的，所述热压的条件为：温度为100-250℃，压力为1.5-20Mpa，时间为5-60分钟。
  12. 根据权利要求6所述的型材，其特征在于以纤维素为主的材料为纸产品，所述纸产品为富含纤维素、半纤维素及木质素的纸产品，所述纸产品的定量为10-400g/m 2、厚度为0.05-1.00mm，优选的，纸产品为60-150g的植物原料来源的纸产品。
  13. 根据权利要求12所述的型材，其特征在于纸产品为原浆板、瓦楞面纸、瓦楞芯纸或牛皮纸中的一种或多种；优选的，纸产品为本色浆板或本色浆纸；优选的，纸产品未经表面涂饰，不加填，不施胶；优选的，纸产品为纸浆中补加酸不溶木质素、合成粘性聚合物粉末或合成粘性聚合物的溶液后抄纸、干燥制备得到的纸产品，优选的，所述型材为各向同性，即所述型材的横向静曲强度和纵向静曲强度的相互差异比例小于30％。
  14. 根据权利要求12-13任一项所述的型材，其特征在于所述型材通过如下制备方法制备得到：利用纸产品即二维生物基材料作为骨架单元，与具有粘胶剂功能的合成粘性聚合物薄膜交错叠放热压成型制备得到型材；或将纸产品喷涂粘性聚合物的溶液或将纸产品浸渍粘性聚合物的溶液，然后烘干得到处理纸产品，然后将处理纸产品叠放或将处理纸产品与纸产品交错叠放，然后热压成型制备得到型材；或在浆料中补加酸化回收的酸不溶木质素，然后抄纸得到处理纸产品，然后将处理纸产品叠放或将处理纸产品和纸产品交错叠放热压成型制备得到型材；或在浆料中添加合成粘性聚合物颗粒或合成粘性聚合物的溶液，然后抄纸得到处理纸产品，然后将处理纸产品叠放或将处理纸产品和纸产品交错叠放热压成型制备得到型材。
  15. 权利要求12所述型材的制备方法，所述制备方法为：利用纸产品即二维生物基材料作为骨架单元，与具有粘胶剂功能的合成粘性聚合物薄膜交错叠放热压成型制备得到型材；或将纸产品喷涂粘性聚合物的溶液或将纸产品浸渍粘性聚合物的溶液，然后烘干得到处理纸产品，然后将处理纸产品叠放或将处理纸产品与纸产品交错叠放，然后热压成型制备得到型材；或在浆料中补加酸化回收的酸不溶木质素，然后抄纸得到处理纸产品，然后将处理纸产品叠放或将处理纸产品和纸产品交错叠放热压成型制备得到型材；或在浆料中添加粘性聚合物颗粒或粘性聚合物的溶液，然后抄纸得到处理纸产品，然后将处理纸产品叠放或将处理纸产品和纸产品交错叠放热压成型制备得到型材，其中纸产品和粘性聚合物的质量比为1：(0.1-1.0)。
  16. 根据权利要求6所述的型材，其特征在于所述以纤维素为主的材料为植物骨架，所述植物骨架为片状植物材料依次经过碱液处理和酸液处理得到，所述粘性聚合物为植物骨架中保留的天然粘性聚合物酸不溶木质素，或者所述粘性聚合物为合成粘性聚合物材料和植物骨架中保留的天然粘性聚合物酸不溶木质素。
  17. 根据权利要求16所述的型材，其特征在于所述植物骨架的制备方法是：将植物材料处理为平均宽度为1-5cm，按加工要求长度的片材，浸泡到浓度在1％wt以上的NaOH溶液中，在低于130℃下蒸煮1-10h，充分破坏细胞膜溶出木质素及可溶性细胞成分后，得到仍保持片状结构和内部孔道贯通的结构单元，然后，将结构单元重新浸泡到饱和木质素盐溶液中使其尽可能吸附后取出浸泡到稀酸溶液充分酸化或者将结构单元直接浸泡到稀酸溶液充分酸化，然后，再洗涤除去盐及小分子有机物，烘干水分得到植物骨架，优选的，植物材料为竹材、木材或秸秆，优选的，所述竹材为3-5年成年竹去竹青竹黄的竹材。
  18. 根据权利要求16所述的型材，其特征在于所述型材的制备方法为：将片状植物材料依次经过碱液处理和酸液处理得到植物骨架，然后添加合成粘性聚合物材料进行热压制备得到型材，优选的，所述热压工艺为：根据所选高分子材料，在100℃以上，3-20Mpa热压，时间为15分钟-24小时。
  19. 根据权利要求18所述的型材，其特征在于所述型材制备方法为：通过热碱溶液蒸煮破坏长尺寸片材的细胞膜，以打通植物细胞间通道，溶出木质素及可溶性细胞成分，得到保持内部空腔和原来形状的竹片材料，再用过量的饱和木质素浸泡溶液使大量木质素进入材料孔隙中，然后取出浸泡好的竹片，再浸入稀酸溶液酸化至内部pH≤4，洗涤除去盐及小分子有机物，然后浸泡于合成粘性聚合物溶液或熔融液中，烘干，可得到保留和更多吸附了天然酸不溶木质素，保留天然骨架结构的三维竹片材料，再单独或堆码，在大于100℃，压力3-20Mpa、时间15分钟-24小时条件下热压，使天然粘性聚合物酸不溶木质素或合成粘性聚合物软化熔融，充满孔隙冷却成型即得到密度大于1，强度超过钢，具有 很强耐腐蚀性和阻燃性能的轻型绿色竹钢或竹型材，其拉伸强度可达400MPa，弹性模量可达到33000Mpa，酸不溶木质素含量为10-30％。
  20. 权利要求16所述型材的制备方法，所述制备方法为：将片状植物材料依次经过碱液处理和酸液处理得到植物骨架进行热压制备得到型材，或者，将片状植物材料依次经过碱液处理和酸液处理得到植物骨架，然后添加合成粘性聚合物材料进行热压制备得到型材，所述热压工艺为：在100℃以上，3-20Mpa热压，时间为15分钟-24小时。
  21. 权利要求1-10、12-14、16-19所述的型材的用途，其特征在于所述型材用于用作支撑结构材料、重组竹/木、金属钢材、高密度纤维板、木塑材料或塑料的替代品。
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