WO2014087053A1

WO2014087053A1 - Method of manufacturing a nanocellulose composite

Info

Publication number: WO2014087053A1
Application number: PCT/FI2013/051139
Authority: WO
Inventors: Kalle NÄTTINEN
Original assignee: Teknologian Tutkimuskeskus Vtt
Priority date: 2012-12-04
Filing date: 2013-12-04
Publication date: 2014-06-12
Also published as: EP2928957A1; FI125900B; FI20126269A; EP2928957A4

Abstract

Nanocellulose composites and a method of manufacturing nanocellulose composites which comprise nanocellulose material mixed with a polymer. The method comprises the steps of milling in a pearl mill a nanocellulose feedstock in liquid phase to produce a dispersion containing nanocellulose. The liquid phase of the dispersion is formed by a monomer of components of a thermoset resin. By adding a hardener the dispersion is hardened to achieve cross-linking of the polymer to the reinforcing nanocellulose. The composite can be used for high-performance composite applications.

Description

Method of manufacturing a nanocellulose composite

Technical Field The present invention concerns a method of manufacturing a nanocellulose composite according to the preamble of claim 1.

According to such a method a nanocellulose feedstock is milled in liquid phase to produce a nanocellulose containing dispersion. The nanocellulose is combined with a polymer component.

The present invention also concerns novel nanocellulose composites.

Background Art

The current production method of nanocellulose is based on milling and fluidisation in water. The energy consumption in the milling is high, 10-20 times higher (50,000 to 100,000 kwh/ton) than in the traditional pulping processes. The process results in an aqueous dispersion of 0.5-2 w-% nanocellulose in water. Production of higher consistencies is not possible due to limitations of the processing, resulting from the hydrogen bonding network formed by the nanocellulose hydroxyl groups and water.

Evaporation of water is not, either, possible without agglomeration of the nanocellulose. If agglomerates are formed, re-dispersion effort equal to original milling is required.

As far as conventional manufacture of nanocellulose is concerned, reference is made to methods known per se, for example, as disclosed in US 2007/0207692, WO 2007/91942, JP 2004204380 and US 7,381,294. JP 2009/292045 discloses a wet dispersing method which includes treating surface-modified cellulose fibres using 0.01-0.5-mm-average-diameter beads to give microfibrils with average fiber diameter from 2 nm to 1.0 μιη. Thus, modifying cellulose fibers with acetic anhydride, adding a dispersing agent of cellulose acetate propionate to a MeCCl₃ solution containing the cellulose acetate fibers, and dispersing the cellulose acetate fibers in a mill gave a dispersion showing fiber average diameter 900 nm.

JP 2009/102630 discloses manufacturing microfibrous cellulose, involves ozonizing cellulose fiber, dispersing the fiber in water to obtain water-based suspension liquid of cellulose fiber, and pulverizing the fiber to obtain microfibrous cellulose with maximum fiber width of 1000 nm or less.

WO 2009081881 discloses manufacture of fibre composites, involving disentangling fiber in pressure homogenizer which is made to eject 100 MPa or more pressure in pressure-reduced condition and/or ultrasonic wave with power density of 1 W/cm² or more in frequency of 15 KHz/1 MHz and conjugating the fiber to matrix material; and disentanglement method of cellulose fiber, which involves irradiating ultrasonic wave to the dispersion liquid of cellulose fiber in which the average of maximum length which is obtained from the plant-derived raw material is 10 μιη to 10 cm.

Summary of Invention

Technical Problem

There are considerable problems relating to the known technology. Thus, transportation of low consistency water dispersions is very inefficient. The high water content and also the hydroxyl functionalities of the cellulose prevent dispersion in thermoplastics and thermoset monomers (which typically react with water)

Suggested methods (freeze drying, filtering) for extraction of water and forming dry nanocomposite are inefficient and not scalable to industrial production.

Attempts have been made to disperse nanocellulose prepared in aqueous media milling into both thermoplastic and thermoset polymers. In thermoplastics, the differences in the polarity of the matrix (non-polar), fibre (highly polar) and water (highly polar) prevent dispersion and reinforcement or require expensive, inefficient surface modifications multiplying the price of the fibre material and resulting in a composition consisting essentially of the

modification/coating - due to high specific surface area of nanocellulose.

In thermosets, some attempts in laboratory to disperse nanocellulose prepared by the standard aqueous milling have been published and protected. However, they require the drying off of the water (99% of composition) and result in agglomerates which need to be re-dispersed by expensive, slow and mostly inefficient methods such as ultrasound. An example of such technology can be found in WO 93/10172. Said publication discloses a process for preparing a composition containing a thermosetting resin and cellulose microfibrils wherein a cellulose source is subjected to a treatment comprising removing the non-crystalline material, dispersing the material to obtain microfibrils and suspending the microfibrils to prevent coagulation. The fibrils are then combined with a thermosetting resin to obtain the desired compound. Solution to Problem

It is an aim of the present invention to provide composite structures of high nanocellulose contents. The invention is based on the idea of producing the composite structures by milling the raw- material of the nanocellulose material in the presence of a monomer of a reactive thermoset polymer. Subsequently, the nanocellulose dispersion so obtained is hardened to form a resin, which optionally can be still further cured. As a result, a nano-cellulosic composite is obtained wherein the nanocellulosic components are cross-bonded to the thermoset polymer components of the composite.

More specifically, the present method is mainly characterized by what is stated in the characterizing part of claim 1.

The present product is mainly characterized by what is stated in the characterizing part of claim 15. Advantageous Effects of Invention

Considerable advantages are obtained by the invention. Thus, the present composites are high performance composites with a biobased reinforcement, in particular a reinforcement based on a material obtained from a renewable source. These materials will provide a substitute or replacement of conventional, expensive, glass and carbon fibre composites which are based on non-renewable materials and which require labour intensive processing and

manufacturing. Further, the present method provides for manufacturing of the reinforcement directly in the would-be composite. Expensive and energy intensive drying of any aqueous dispersion, as conventionally called for, is avoided. Agglomeration of the nanocellulose during such a drying process can also be avoided. There is no need for manual hand lay-up processing related to long- fibre composites by using the present technology of nano-scale reinforcement of the composites. There will be formed a strong cross- linking of the cellulosic fibres to the polymer matrix, based on covalent bonds between the components.

Experiments performed show that in less polar solvents or other media the milling can be done at 20-50 times the consistency that is possible with water. The consistency can be further raised by centrifugal concentration to a level sufficient or even above the ideal reinforcement contents in the following be composite structure. Due to the low viscosity of the dispersions (in contrast with the water-nanocellulose dispersions), they can be applied by liquid pumping methods such as those in resin transfer molding (RTM) processing. Description of Embodiments

Next embodiments are discussed more closely with reference to the manufacture of reinforced thermoset resins using pearl mills or basket mills. As referred to in the above discussion, in the present invention, a suitable raw-material, such as macroscopic cellulose, for the target nanocellulose material, is combined at a

predetermined ratio with a component of or a mixture of components of a thermoset resin. In the following the "component(s)" will also be referred to as "resin precursors". The feeds are milled together such as to achieve cross-linking at least essentially based on covalent bonds or similar chemical bonds. Some physical bonds may also be formed during the processing. In an advantageous embodiment the conditions of the milling are non-aqueous. In particular, essentially water- free processing is considered a highly preferred embodiment. Water- free conditions will assist in avoiding the problems relating to drying of the nano-cellulosic material. The cellulose raw-material and the resin precursor(s), for example, monomer(s), are subjected to milling in, for example, a pearl mill or basket mill or a similar mill capable of exerting milling or grinding forces for diminishing the size of the raw-material into nano-size scale.

In a pearl mill there are typically grinding pearls, typically ceramic beads, or sand particles which provide the grinding effect. Typically, the average diameter of the pearls or beads is about 0.01-0.5-mm.

In a basket mill there is atypically a hub with agitator pins. Said pins create a high-energy zone or a vortex within a basket, and when the material is fed into the basket it will pass through the vortex it will be subjected to the high-energy action.

The energy consumption of the milling is typically 10,000 to 100,000 kwh/ton.

The nanocellulose can be synthesised from various cellulosic materials, such as wood, agrofibres, such as annual plants, and food production side-streams.

The cellulose feedstock is preferably chemically pretreated and purified.

Thus, in one embodiment, the raw-material of the nanocellulose comprises macroscopic cellulose, for example cellulosic fibres, in particular cellulosic fibres obtained by defibering of lignocellulosic raw-material, optionally bleached. Vegetal (annual or perennial) fibres instead of wood are another interesting material source; for example nanofibers separated from a residue from carrot juice production, are highly homogeneus nanofibers with better mechanical properties than wood nanofibers. The obtained nanocellulose is in the form of fibres with a diameter between 1.5-5 nm and length up to several micrometers.

In the present context, "nano-scale" stands for a smallest size of the particles amounting to about 1 to 950 nm, in particular about 10 to 900 nm, for example about 20 to 500 nm, typically about 25 to 200 nm. In particular, the raw-material is diminished such that at least 5 %, preferably at least 10 %, in particular at least 20 % of the particles exhibit a smallest dimension in the nano-scale range.

In one embodiment, "nanocellulose" refers to any cellulose fibers with an average (smallest) diameter (by weight) of 10 micrometer or less, preferably 1 micrometer or less, and most preferably 200 nm or less. The "cellulose fibers" can be any cellulosic entities having high aspect ratio (preferably 100 or more, in particular 1000 or more) and in the above-mentioned size category. These include, for example, products that are frequently called fine cellulose fibers, microfibrillated cellulose (MFC) fibers and cellulose nanofibers (NFC). Common to such cellulose fibers is that they have a high specific surface area, resulting in high contact area between fibers in the end product. As a result dispersed NFCs will form networks within polymer matrices.

The aspect ratio of the nanocellulose is typically greater than 5. Typically milling is carried out in liquid phase, i.e. in the liquid phase formed by the component(s) of the thermoset resin. Thus, in one embodiment, the liquid phase resin precursor(s) - for example monomer(s) - of the thermoset are first added to the mixing space of the mill In one embodiment, a liquid dispersion is formed having a consistency (solid matter content based on the total weight of the dispersion) of at least about 0.01 %, preferably about 0.1 to 50 %, in particular about 0.2 to 25 %, for example about 0.3 to 20 %, typically about 0.5 to 15 %. Milling is continued until a sufficient reduction in dimension of the cellulose has been achieved.

Optionally, the liquid dispersion can be heated to lower the viscosity and to enhance the process. The heating can be carried out before addition of the raw-material, in practice the cellulose material, or during the addition or at intervals between additions of the raw-material.

Typically, temperatures in excess of room temperature can be used, for example at least 30 °C, in particular at least 35 °C, for example 40 to 100 °C, in particular about 45 to 90 °C, at ambient pressure. The heating is preferably carried out at a temperature below the boiling point of the liquid precursor at the prevailing pressure.

Typically, milling is carried out in ambient pressure in an open vessel. Naturally, by suitable modifying the milling equipment, operation at increased pressures of, for example 1.1 to 15 bar(a) is also possible.

Following the milling step, a second component of the thermoset along with further additive(s), if any, is added to the dispersion. The second component is typically a hardener which achieves the cross-linking of the monomer and, thus, setting of the thermoset. The addition of the second component of the thermoset along with further additive(s) is preferably carried out in a separate mixing step. This mixing can be carried out in the same equipment or in a separate mixing or blending unit. Mixing is continued to allow for the formation of a resin.

Finally, the resin thus obtained can be further treated and used in various fashions.

For example, the resin can be transferred to a mold. It can be impregnated to a fibre structure. It can be applied as a coating on a substrate surface.

As mentioned above, additional benefits of the present technology are obtained by

replacement of hand- lay up processing in fibre composites with a 100 % liquid injection based system.

Further setting and curing of the material or composite can be achieved by applying heat. Typically, temperatures in excess of room temperature are applied, for example at least 30 °C, in particular at least 50 °C, for example 60 to 400 °C, in particular about 100 to 350 °C. The thermoset monomers used herein include for example polyols of polyester resins and epichorohydrin of epoxy resins.

For epoxy resins, the hardener is typically a polyfunctional curative. Basically, a molecule containing reactive hydrogen may react with the epoxide groups of the epoxy resin. Hardeners for epoxy resins can be selected from the group consisting of amines, acids, acid anhydrides, phenols, alcohols and thiols.

As known in the art, there are some combinations of epoxy resins and hardeners which will cure at ambient temperature, but in practice many require additional heat, a typical hardening temperature being higher than to 100 °C, in particular higher than 150 °C, for example up to a maximum of about 200 °C for most of the systems.

In the case of polyester resins, the polyol is typically a glycol, such as ethylene glycol, which is combined with an acid, such as phthalic acid or maleic acid. Hardening is achieved by creating free radicals at the unsaturated bonds of the material. The free radicals can be induced by adding a compound that easily decomposes into free radicals, such as an organic peroxide, for example benzoyl peroxide or methyl ethyl peroxide.

The resin can be photocurable.

Summarizing the above, nanocellulose will be produced by pearl milling of chemically pretreated and purified cellulose in the pre-polymer using polyester and epoxy resins. Both the polyester and epoxy resins readily react with the cellulose fibre surface hydroxyl groups, resulting in a cross-linked composite structure where the reinforcement fibre is integrally bound and its full potential may be exploited - without surface modification. Industrial Applicability

The present composites are useful for high-performance composite applications. The current, strong trend of automotive industry to reduce the weight of structures by replacing metals with FR composites. A drawback of known composites has been their high price and difficult recycling. With the present technology, these problems can be overcome.

Other applications include uses in the fields of, for example, aeronautics and aerospace, sports equipment, coatings and lacquers, glues and adhesives.

Citation List

Patent Literature US 2007/0207692

WO 2007/91942

JP 2004204380

US 7,381,294

JP 2009/292045

JP 2009/102630

WO 2009081881

WO 93/10172

Claims

Claims:

1. Method of manufacturing nano cellulose composites which comprise nano cellulose material mixed with a polymer, comprising the steps of

- milling a nanocellulose feedstock in liquid phase to produce a nanocellulose

containing dispersion, said liquid phase being formed by a component or a mixture of components of a thermoset resin, and

- hardening the dispersion.

2. The method according to claim 1, wherein the nanocellulose dispersion is combined with a hardening component of the thermoset resin.

3. The method according to claim 1 or 2, wherein the raw-material of the nanocellulose comprises macroscopic cellulose, for example cellulosic fibres, in particular cellulosic fibres obtained by defibering of lignocellulosic raw-material, optionally bleached.

4. The method according to any of claims 1 to 3, wherein the nanocellulose raw-material is combined at a predetermined ratio with a resin precursor or a mixture of precursors.

5. The method according to any of the preceding claims, wherein the feeds are milled together such as to achieve cross-linking at least essentially based on covalent bonds or similar chemical bonds.

6. The method according to any of the preceding claims, wherein the conditions of the milling are non-aqueous, preferably essentially water- free.

7. The method according to any of the preceding claims, wherein the cellulose raw-material and the precursor(s) of the resin are subjected to milling in a pearl mill or basket mill or a similar mill capable of exerting milling or grinding forces for diminishing the size of the raw- material into nanosize scale.

8. The method according to any of the preceding claims, wherein a liquid dispersion is formed having a consistency of at least about 0.01 %, preferably about 0.1 to 50 %, in particular about

0.2 to 25 %, for example about 0.3 to 20 %, typically about 0.5 to 15 %, expressed as solid matter content based on the total weight of the dispersion.

9. The method according to any of the preceding claims, wherein the liquid dispersion is heated to lower the viscosity and to enhance the process.

10. The method according to any of the preceding claims, wherein the liquid phase of the dispersion is formed by a precursor of the thermoset resin, such as a monomer.

11. The method according to any of the preceding claims, wherein the component or a a second component of the thermoset along with further additive(s), if any, is added to the dispersion in particular to achieve cross-linking of the monomer.

12. The method according to claim 10, wherein the reinforced resin is transferred to a mold, it is impregnated to a fibre structure, or it is applied as a coating on a substrate surface, or a combination thereof.

13. The method according to any of the preceding claims, wherein the resin precursor is a monomer selected from polyols of polyester resins and epichorohydrin of epoxy resins.

14. The method according to any of the preceding claims, wherein the nanocellulosic feedstock is formed by cellulose fibers with an average smallest diameter of 10 micrometer or less, preferably 1 micrometer or less, and most preferably 200 nm or less.

15. A nanocellulose composite obtained by a method as defined in any of claims 1 to 14.

16. A nanocellulose composite according to claim 15, comprising a nano-cellulosic composite wherein the nanocellulosic components are cross-bonded to the thermoset polymer components of the composite.