U.S. patent application number 09/341487 was filed with the patent office on 2001-07-26 for intermediate product for manufacturing ligin polymers and it's use in manufacturing reagents for making composite materials from plant fibres, waterproof papers and cardboards,and thermosetting plastics from derivatives.
Invention is credited to BRAUN-LULLEMANN, ANNETTE, FASTENRATH, MERIE, HUTTERMANN, ALOYS, MAI, CARSTEN, MAJCHERCZYK, ANDRZEJ, NOETZOLD, SONJA.
Application Number | 20010009955 09/341487 |
Document ID | / |
Family ID | 27217024 |
Filed Date | 2001-07-26 |
United States Patent
Application |
20010009955 |
Kind Code |
A1 |
HUTTERMANN, ALOYS ; et
al. |
July 26, 2001 |
INTERMEDIATE PRODUCT FOR MANUFACTURING LIGIN POLYMERS AND IT'S USE
IN MANUFACTURING REAGENTS FOR MAKING COMPOSITE MATERIALS FROM PLANT
FIBRES, WATERPROOF PAPERS AND CARDBOARDS,AND THERMOSETTING PLASTICS
FROM DERIVATIVES
Abstract
The invention relates to an intermediate product for
manufacturing polymers of lignin derivatives from the pulp
industry, made by treating the lignin derivatives with phenol
oxidizing enzymes in the presence of oxidation agents,
characterized in that the lignin derivatives are (a) subjected to
enzyme treatment for more than 3 hours in the presence of air, or
(b) subjected to enzyme treatment for more than 10 minutes while
air or oxygen is being passed through them, or (c) oxidized by
treatment with chemical oxidation agents. The intermediate product
is used in manufacturing polymers of lignin derivatives from the
pulp industry, fiber-reinforced thermosetting composite materials
from plant fibers, waterproof papers and cardboards, and
thermosetting plastics from lignin derivatives.
Inventors: |
HUTTERMANN, ALOYS;
(GOTTINGEN, DE) ; MAJCHERCZYK, ANDRZEJ;
(GOTTINGEN, DE) ; MAI, CARSTEN; (GOTTINGEN,
DE) ; BRAUN-LULLEMANN, ANNETTE; (BOVENDEN, DE)
; FASTENRATH, MERIE; (GOTTINGEN, DE) ; NOETZOLD,
SONJA; (GOTTINGEN, DE) |
Correspondence
Address: |
PROSKAUER ROSE
1585 BROADWAY
NEW YORK
NY
10036
|
Family ID: |
27217024 |
Appl. No.: |
09/341487 |
Filed: |
February 4, 2000 |
PCT Filed: |
January 19, 1998 |
PCT NO: |
PCT/EP98/00254 |
Current U.S.
Class: |
527/403 ;
530/500 |
Current CPC
Class: |
C08L 97/02 20130101;
D21H 19/14 20130101; C08H 8/00 20130101; C08H 6/00 20130101; C12P
7/22 20130101; C08L 2666/26 20130101; D21H 21/20 20130101; C09D
197/005 20130101; C08L 97/02 20130101; C08L 97/005 20130101 |
Class at
Publication: |
527/403 ;
530/500 |
International
Class: |
C08G 002/00; C08L
097/00 |
Foreign Application Data
Date |
Code |
Application Number |
Jan 14, 1997 |
DE |
197 00 902.6 |
Jan 14, 1997 |
DE |
197 00 904.2 |
Jan 14, 1997 |
DE |
197 00 906.9 |
Claims
1. Method for manufacturing polymers of lignin derivatives from the
pulp industry by treating the lignin derivatives with phenol
oxidizing enzymes in the presence of oxidation agents,
characterized in that the lignin derivatives are (a) subjected to
enzyme treatment for more than 3 hours in the presence of air, or
(b) subjected to enzyme treatment for more than 10 minutes while
air or oxygen is being passed through them, or (c) oxidized by
treatment with chemical oxidation agents, and that the activated
intermediate product thus obtained is caused to react with
non-activated lignin derivatives while polymeric lignin products
are formed.
2. Method according to claim 1, characterized in that the lignin
derivatives are kraft lignin and lignin sulfonate.
3. Method according to claim 1, characterized in that the phenol
oxidizing enzymes are phenol oxidase and laccase.
4. Method according to claim 1, characterized in that the enzyme
treatment according to step (a) is performed for more than 15
hours.
5. Method according to claim 1, characterized in that the enzyme
treatment according to step (b) is performed for more than 30
minutes.
6. Method according to claim 1, characterized in that the activated
intermediate product or its solution is isolated.
7. Use of the products made with the method described in claims 1
to 6 in manufacturing polymers of lignin derivatives from the pulp
industry.
8. Use according to claim 7 for manufacturing highly active
reagents for making fibre-reinforced thermosetting composite
materials of plant fibres.
9. Use according to claim 7 for manufacturing waterproof papers and
cardboards.
10. Use according to claim 7 for manufacturing highly active
reagents for making thermosetting plastics from lignin derivatives.
Description
[0001] The present invention relates to an intermediate product for
manufacturing polymers from lignin derivatives which are
by-products of the pulp industry, and to the use of these
intermediate products in manufacturing highly reactive reagents for
making composite materials from plant fibres, waterproof paper and
cardboards, and thermosetting plastics from lignin derivatives.
[0002] DE 37 992 C2 describes a method for manufacturing a binding
agent for wood products, using phenolic substances, in particular
lignin sulfonate, whereby enzymes are added to the phenolic
substance to activate same, the phenols polymerize according to a
radical mechanism, while the phenolic substance is converted into
an active binding agent. It is known that this reaction takes place
in the presence of oxygen, such as atmospheric oxygen, but until
now, such an activated binding agent has not been caused to react
with oxygen for a long period of time or by intensive aeration.
[0003] Surprisingly it was found that lignin derivatives from the
pulp industry, such as kraft lignin or lignin sulfonate, with
phenol oxidizing enzymes such as phenol oxidase or laccase, form a
particularly reactive lignin product as an intermediate product
when caused to react for a long period of time or intensively with
oxygen, air or other chemical oxidizing agents. This intermediate
product can be isolated and stored for a long time, and it further
reacts with other non-activated lignin derivatives to form a
polymer of high molecular weight. The intermediate product can be
characterized in that the material is caused to react with laccase.
After that reaction, it shows a typical ESR spectrum with a signal
for phenoxyradicals in the range of about 3400 gauss, which,
however, does not remain constant as a typical radical signal.
However, surprisingly, the increased reactivity of the intermediate
product remains intact even after long periods of time, for example
for months. This means that this activated intermediate product is
considerably more active when caused to react with phenol oxidizing
enzymes than non-treated lignin derivatives, and that the typical
ESR spectrum is therefore formed at a considerably higher intensity
than lignin derivatives not treated in that manner.
[0004] The intensity of the signal of the activated intermediate
product is at least five times that of the signal of the lignin
derivative serving as the initial product. For example, the signal
is measured under the following conditions:
[0005] 77.degree. K.; 9.5 GHz; ESR attenuation 20 dB; mod. frequ.
100 MHz, mod. amplitude 4.0 gauss.
[0006] The activated intermediate product can be obtained when
technical lignins such as lignin sulfonates, kraft lignin,
organosolve lignin, acetosolve lignin, ASAM lignin, etc., which are
pulp industry by-products, are treated for a long time with air or
oxygen in the presence of phenol oxidizing enzymes. Even after a
period of about three hours, for example, but especially after 15
or 20 hours, the phenoxyradical signal can be found to increase.
When air or oxygen are passed through under pressure, the increased
signal occurs after a significantly shorter period of time, namely
after 10 minutes or, as an example, after about 30 minutes.
[0007] The intermediate product can also be obtained with chemical
oxidizing agents. For example, potassium permanganate, bichromate
or ozone, which are customary agents in lignin chemistry, can serve
that purpose.
[0008] The enzymatic formation of the activated intermediate
product is possible only when large amounts of oxygen are present.
Since at room temperature, oxygen dissolves in water only at the
rate of 9 mg/L, the formation of the intermediate product is
encouraged only when more oxygen is added, either through aeration
or in the form of oxidation agents. Even when it takes a long time
for the oxygen equilibrium to be established, enough oxygen may
have acted upon the lignin derivative after some time.
[0009] In the presence of phenol oxidizing enzymes, the activated
intermediate product reacts with non-activated lignin derivatives
that may be obtained, for example, in pulp production. This is
accompanied by the formation of polymeric lignin products, whereby
the molecular weights are considerably higher than those obtained
when phenol oxidizing enzymes act upon lignin derivatives without
the presence of activated lignin derivatives. They are generally at
least twice as high.
[0010] The lignin polymers obtained in the polymerization of lignin
derivatives in the presence of active intermediate products can be
used for making highly active reagents for the manufacture of
composite materials from plant fibres, waterproof papers and
cardboards, and thermosetting plastics from lignin derivatives. It
is thus possible for the first time to produce fibre-reinforced
thermosetting plastics from renewable raw materials completely by
in situ polymerization.
[0011] In comparison with the lignin used as the initial material,
the activated lignin has an ESR spectrum in which the
phenoxyradical signal is of considerably higher intensity. This is
demonstrated by FIGS. 1 and 2. FIG. 1 shows an ESR spectrum of 1%
lignin sulfonate with an addition of laccase (4 U/ml) after 30
minutes of incubation without oxygen treatment. FIG. 2 shows the
corresponding spectrum of lignin sulfonate which was incubated with
laccase for 20 hours under increased oxygenation and then
autoclaved and stored for three months. Following renewed
incubation with laccase (4 U/ml, 30 min. incubation without oxygen
treatment), a comparison between the strongest signal at about 3400
gauss and the background signals shows that the intensity of the
phenoxyradical signal was at least five times as strong as in FIG.
1.
[0012] So high is the reactivity of the resulting intermediate
product that even lignin sulfonate, a polymer of extremely high
water solubility, forms a water-insoluble product.
[0013] The intention is described below by means of the
examples:
EXAMPLE 1
[0014] We dissolved 20 g of lignin sulfonate in 80 ml of Mcllvaine
buffer, pH 5.5, and added 800 U/ml laccase. We shook the solution
for 20 hours in a 500 ml erlenmayer flask at 37.degree. C. in a
water bath. Then we autoclaved the solution. We stored the
resulting lignin sulfonate for two months. Following renewed
incubation with laccase (4 U/ml, 30 min. incubation without oxygen
treatment), the ESR spectrum was as in FIG. 2.
EXAMPLE 2
[0015] To activated lignin sulfonate according to Example 1, we
added kraft lignin at the ratio of 1:10 and suspended with a
concentration of 100 mg/10 ml in buffer, and incubated for 6 hours
with laccase (500 U/ml in a sealed test tube, without special
oxygen treatment. Simultaneously, we carried out corresponding
control tests with non-activated lignin and incubated without
laccase. Then we isolated the resulting lignins and measured the
molecular weight distribution in the HPLC.
[0016] The following molecular weights were determined:
1 non-activated kraft lignin 5,400 g/mol non-activated kraft lignin
incubated with laccase 6,300 g/mol non-activated kraft lignin plus
activated lignin 6,000 g/mol without laccase non-activated kraft
lignin plus activated lignin 11,000 g/mol incubated with
laccase
EXAMPLE 3
[0017] We adjusted a lignin suspension consisting of
[0018] 80 ml of Mcllvain buffer, pH 4.5
[0019] 16.5 g of kraft lignin
[0020] 4 g lignin sulfonate
[0021] with concentrated laccase to a final concentration of 800
U/ml, aerated with compressed air for 3 hours and stirred. We
applied the solution thus obtained to a cotton fabric commonly used
in the manufacture of thermoplastic composite materials of
renewable raw materials, and air-dried it. Our subsequent
examination of the product showed a 42% degree of adhesion
(absolutely dry lignin in relation to absolutely dry fibre).
[0022] To determine the bonding rate of the applied lignin, we
incubated the coated fabric for three hours in water or in 0.1 m of
NaOH and subsequently determined the volume of dissolved lignin.
After water treatment, 2% (w/w) and after alkali treatment, 30%
(w/w) of the applied lignin peeled off the cotton fibre again.
EXAMPLE 4
[0023] In a high vacuum, we sprinkled gold onto cotton fibre coated
according to the method described in Example 3 and examined it
under a scanning electron microscope.
[0024] FIGS. 3, 4 and 5 show that an intimate bond can be
recognized between the coating and the fibre without a transitional
zone being visible. This shows that the coating is caused by a true
covalent bond between the lignin and the fibre surface.
EXAMPLE 5
[0025] We adjusted 20% lignin glue consisting of
[0026] 80 ml of Mcllvain buffer, pH 4.5
[0027] 16.5 g of kraft lignin
[0028] 5 g of lignin sulfonate
[0029] with concentrated laccase to a final concentration of 800
U/ml, aerated with compressed air for 3 hours and stirred. After 3
hours, we diluted the solution thus obtained with a laccase
solution (800 U/ml in buffer, pH 4.5) at a ratio of 1.+-.4 and
applied it to both sides of a filter paper.
[0030] We air-dried the treated papers overnight. The papers had a
coating ratio of 9% weight-by-weight lignin to weight-by-weight
paper.
[0031] We then measured the resistance of the coating to water and
0.1 M NaOH and determined the water absorption rate.
[0032] A three-hour incubation in water caused 3% of the applied
amount of lignin to peel off; incubation for the same period in 0.1
N.sup.3 NaOH caused 31% of the lignin to peel off the paper
surface.
[0033] In comparison with the uncoated controls, the coated papers
had a water absorption rate that was 30% lower. Water tear
resistance was clearly improved: while the untreated paper
dissolved into individual fibres, the coated paper was still
completely intact.
EXAMPLE 6
[0034] In a high vacuum, we sprinkled gold onto paper coated
according to the method described in Example 3 and examined it
under a scanning electron microscope.
[0035] FIG. 6 shows that an intimate bond can be recognized between
the coating and the paper fibre without a transitional zone being
visible. This shows that the coating is caused by a true covalent
bond between the lignin and the fibre.
EXAMPLE 7
[0036] We adjusted a solution consisting of 80 ml of Mcllvain
buffer, pH 4.5, and 16.5 g of lignin sulfonate with concentrated
laccase to a final concentration of 800 U/ml, and shook it for 25
hours at 37.degree. C. in a water bath. During the last few hours,
the molecular weight (measured in the HPLC) as well as the
viscosity of the solution increased sharply (FIG. 7). The product
thus obtained was insoluble in water, 0.1 m NaOH and in the
customary organic solvents such as ethanol, ether, acetone or ethyl
acetate.
* * * * *