U.S. patent application number 13/818036 was filed with the patent office on 2015-07-23 for non-phthalic plasticiser.
This patent application is currently assigned to Perstorp AB. The applicant listed for this patent is Hakan Bjornberg, Karin Ohgren Gredegard, Anders Magnuesson, Niklas Persson, Maria Peterson, Kent Sorensen. Invention is credited to Hakan Bjornberg, Karin Ohgren Gredegard, Anders Magnuesson, Niklas Persson, Maria Peterson, Kent Sorensen.
Application Number | 20150203657 13/818036 |
Document ID | / |
Family ID | 45723674 |
Filed Date | 2015-07-23 |
United States Patent
Application |
20150203657 |
Kind Code |
A1 |
Gredegard; Karin Ohgren ; et
al. |
July 23, 2015 |
NON-PHTHALIC PLASTICISER
Abstract
The present invention refers to a plasticiser, said plasticiser
being an ester formed by reaction of a pentaerythritol and a
monocarboxylic acid, having 4-5 carbon atoms. In a further aspect
the present invention refers to the use of said plasticiser in
blends and in a PVC resin. The plasticiser of the present invention
is a non-phthalic plasticiser that has proven to have shorter
fusion time and higher plasticising efficiency compared to
commercial non-phthalic PVC plasticisers.
Inventors: |
Gredegard; Karin Ohgren;
(Lund, SE) ; Magnuesson; Anders; (Bjarnum, SE)
; Bjornberg; Hakan; (Angelholm, SE) ; Persson;
Niklas; (Hoganas, SE) ; Peterson; Maria;
(Hoor, SE) ; Sorensen; Kent; (Perstorp,
SE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Gredegard; Karin Ohgren
Magnuesson; Anders
Bjornberg; Hakan
Persson; Niklas
Peterson; Maria
Sorensen; Kent |
Lund
Bjarnum
Angelholm
Hoganas
Hoor
Perstorp |
|
SE
SE
SE
SE
SE
SE |
|
|
Assignee: |
Perstorp AB
Perstorp
SE
|
Family ID: |
45723674 |
Appl. No.: |
13/818036 |
Filed: |
July 26, 2011 |
PCT Filed: |
July 26, 2011 |
PCT NO: |
PCT/SE2011/000138 |
371 Date: |
January 16, 2015 |
Current U.S.
Class: |
524/111 ;
106/505; 560/81 |
Current CPC
Class: |
C08K 5/092 20130101;
C08J 3/18 20130101; C07C 69/33 20130101; C07C 69/34 20130101; C08K
5/11 20130101; C08K 5/1535 20130101; C08K 5/103 20130101; C08K 5/12
20130101; C08K 5/092 20130101; C08L 27/06 20130101; C08K 5/12
20130101; C08L 27/06 20130101; C08K 5/103 20130101; C08L 27/06
20130101 |
International
Class: |
C08K 5/103 20060101
C08K005/103; C08K 5/11 20060101 C08K005/11; C07C 69/34 20060101
C07C069/34; C08K 5/1535 20060101 C08K005/1535 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 23, 2010 |
SE |
1000853.0 |
Claims
1. A plasticiser, said plasticiser comprising an ester formed by
reaction of a polyol and a monocarboxylic acid, characterised in
that said ester has a general formula (1) of ##STR00002## where
R.sup.1, R.sup.2, R.sup.3 and R.sup.4 represent --O--CO-alkyl
groups containing 4-5 carbon atoms, wherein said polyol is
pentaerythritol and wherein said --O--CO-alkyl group is selected
from the group consisting of butyrate, valerate and a mixture
thereof.
2. A plasticiser according to claim 1, characterised in that at
least one of said --O--CO-alkyl groups is butyrate.
3. A plasticiser according to claim 1, characterised in that at
least two of said --O--CO-alkyl groups are butyrates.
4. A plasticiser according to claim 1, characterised in that at
least three of said --O--CO-alkyl groups are butyrates.
5. A plasticiser according to claim 1, characterised in that said
monocarboxylic acid is butyric acid.
6. A plasticiser according to claim 1, characterised in that said
monocarboxylic acid is valeric acid.
7. A plasticiser blend, characterised in that 1-20 parts by weight
of a plasticiser according to any of the claims 1-6 is blended with
1-20 parts by weight of an oligo ester of 2-ethylhexanol and
furandicarboxylic acid.
8. A plasticiser blend according to claim 7, characterised in that
1-5 parts by weight of a plasticiser according to any of the claims
1-6 is blended with 1-5 parts by weight of an oligo ester of
2-ethylhexanol and furandicarboxylic acid.
9. A plasticiser blend according to claim 7, characterised in that
1-2 parts by weight of a plasticiser according to any of the claims
1-6 is blended with 1-2 parts by weight of an oligo ester of
2-ethylhexanol and furandicarboxylic acid.
10. Use of a plasticiser according to any of the claims 1-9 in a
PVC resin.
11. Use of a plasticiser according to claim 10 with pentaerythritol
adipate as co-stabiliser.
Description
[0001] The present invention refers to a plasticiser, said
plasticiser being an ester formed by reaction of a polyol and a
monocarboxylic acid, preferably having 4-5 carbon atoms. In a
further aspect the present invention refers to the use of said
plasticiser in a PVC resin.
[0002] Plasticisers have the ability to reduce the glass transition
temperature of polymers and thereby provide soft and/or flexible
products, contrary to the hard and brittle basic material. Organic
esters constitute the major group of poly(vinyl chloride) (PVC)
plasticisers. Among these organic esters phthalates are without
competition the largest subgroup. The most commonly used phthalate
esters as PVC plasticisers are di-2-ethylhexyl phthalate (DEHP),
also known as dioctyl phthalate (DOP), diisononyl phthalate (DINP)
and diisodecyi phthalate (DIDP). Further examples of organic esters
used as PVC plasticisers are adipates, trimellitates, sebacates and
azelates. Phosphate esters, such as tris(2-ethyihexyl)phosphate,
and sulphonate esters, such as arylesters of sulphonic acids, are
used in minor amounts. The preparation and the use of said
plasticisers are well known and thoroughly disclosed in a number of
handbooks and encyclopedias of chemical technology.
[0003] Plasticized PVC is used in a multitude of plastic items
going to a multitude of end-user sectors such as flexible films,
cables and wires, flooring, flexible tubes and profiles and coated
fabric and paper. Over the last few decades, the use of plastics as
packaging materials has increased due to their properties and
processability. As a result of contact between packed food and
plastics, traces of plasticisers may migrate into the food
contaminating it and affecting consumers' health. The situation has
created an increasing desire for phthalate-free plasticisers for
applications like toys, food contact materials, medicals and other
applications where the use of phthalates are either restricted or
non-wanted by end-users.
[0004] Di-2-ethyl hexyl phthalate (DEHP) is often called dioctyl
phthalate and abbreviated DOP. It is the most important phthalate,
being the diester of phthalic acid and 2-ethylhexanol. Due to its
suitable properties and the low cost, DOP is widely used as a
plasticiser in PVC articles. Plastics may contain 1% to 40% of DOP.
Both technically and commercially it is the reference against which
other plasticisers are assessed. DOP is used in nearly all
application areas for plasticised PVC. Technical limits on its use
are imposed by considerations of volatility and migration. DOP is
associated with health risks since it has a low vapour pressure and
the temperatures for processing PVC articles are often high,
leading to release of high levels. DOP can be absorbed from food
and water. It can also leach into a liquid that comes in contact
with the plastic.
[0005] On 28 Oct. 2008, the European Chemicals Agency published a
list of the first substances to enter onto the REACH authorisation
"candidate list". As expected, three phthalates, di-2-ethylhexyl
phthalate (DEHP or DOP), di-n-butyl phthalate (DBP) and butyl
benzyl phthalate (BBP), were included on the list due to their EU
hazard classification. The inclusion of DEHP, DBP and BBP on the
"candidate list" for authorisation means that any supplier of an
article containing more than 0.1% weight by weight (w/w) of them
now has an obligation to provide information to the recipient of
that article. Further down the supply chain, retailers also have an
obligation to provide the same information to consumers, but only
if a consumer requests it. According to the general view
non-labelled phthalates (for instance DINP, DIDP and DPHP
(dipropylheptyl) phthalate) will take over after DOP and other
labelled phthalates. Long term risk assessment studies in the
European Union have largely cleared DINP and DIDP and they are
viewed as cost-effective substitutes to DOP. However, non-labelled
phthalates are represented by the bad press surrounding the name
"phthalates".
[0006] Various alternative plasticisers such as adipates,
trimellitates, citrates, benzoates esters, "bioplasticisers" have
been evaluated, but none being currently viewed as "the" substitute
for commercial phthalates. They are mostly hindered by a high price
as well as in some cases poorer performance. The situation has
created a market desire for a competitively priced, well
performing, environment-friendly non-phthalic plasticiser.
[0007] One of the most widely used phthalate substitute today is
Hexamoll.RTM. DINCH (BASF's tradename for 1,2-cyclohexane
dicarboxylic acid diisononyl ester). Hexamoll.RTM. DINCH (in the
following text denoted DINCH) is a non-phthalic plasticiser that
has been developed for the manufacture of flexible plastic articles
in sensitive application areas such as toys, medical devices and
food packaging. From a chemical point of view it belongs to the
group of aliphatic esters.
[0008] Aliphatic esters of polyfunctional alcohols exhibit a number
of advantages compared to for example aromatic esters, such as
above phthalates constituting the majority of plasticisers used
today. The aliphatic structure implies the possibility of improved
stability towards outdoor exposure. Furthermore, they exhibit a
reduced tendency to generate fire smoke. Said aliphatic esters also
exhibit, when raw materials are properly chosen, a reduced
volatility and are hence emitted to the environment in lower
amounts. Said esters often exhibit an increased biodegradability
compared to aromatic esters, like phthalates, why the environmental
impact is reduced. Aliphatic esters are further judged to have less
impact on living organisms than phthalates. This type of esters has
due to high thermal and oxidation stability as well as due to said
biodegradability a long time use in lubricants. Said esters have,
however, a limited use as plasticisers mainly because of their
limited compatibility with PVC. U.S. Pat. No. 3,939,201 teaches
triesters of triethanolmethane and an acid component consisting of
a monocarboxylic acid preferably having 6-8 carbon atoms such as
the exemplified 2-ethylhexanoic acid. European Patent No. 0739377
teaches a plasticised PVC composition consisting essentially of a
pentaerythritol ester of a mixture of C5 and C7 alkyl carboxylic
acids and 3,5,5-trimethylhexanoic acid. The International Patent
Application No. 01/00722 relates to a plasticiser for polymeric
composition, preferably PVC. The plasticiser comprises at least one
polyolester obtainable by addition of at least one aromatic
monocarboxylic acid and/or at least one aliphatic monocarboxylic
acid having 2-5 carbon atoms and at least one aliphatic
monocarboxylic acid having 6-12 carbon atoms to an aliphatic
polyalcohol having three or more hydroxyl groups. European Patent
No. 1353988 discloses the use of a trimethylolpropane ester-based
multi-component composition as plasticiser.
[0009] An aliphatic ester according to the present invention has
shown to be a very well performing non-phthalic plasticiser for
PVC. Better than commercial non-phthalic plasticisers like DINCH
and in several aspects even better than phthalates like DOP, DPHP
and DINP. In comparison with DINCH, DOP, DPHP and DINP the
plasticiser of the present invention has proven to be a more
efficient PVC plasticiser. The fusion time is shorter, i.e. the
compatibility with PVC is higher and the plasticising effect is
higher, i.e. the same plasticising effect can be obtained with a
smaller amount of plasticiser. Migration and chemical resistance
are also significantly improved relative to the phthalates and
DINCH. The present invention thus provides a more efficient and
environmental-friendly alternative to the commercial phthalic PVC
plasticizers mentioned above and the commercial non-phthalic PVC
plasticizer DINCH. The present invention accordingly refers to a
plasticiser, said plasticiser being an ester formed by reaction of
a polyol and a monocarboxylic acid. Said ester has a general
formula (1) of
##STR00001##
wherein, R.sup.1, R.sup.2, R.sup.3 and R.sup.4 represent
--O--CO-alkyl groups containing 4-5 carbon atoms.
[0010] Said --O--CO-alkyl group is butyrate, valerate or a mixture
thereof. In one embodiment of the present invention at least one of
said --O--CO-alkyl groups is butyrate. In another embodiment of the
present invention at least two of said --O--CO-alkyl groups are
butyrates and in yet another embodiment at least three of said
--O--CO-alkyl groups are butyrates.
[0011] The plasticiser of the present invention is preferably an
ester formed by reaction of pentaerythritol and a monocarboxylic
acid. Said monocarboxylic acid preferably being butyric or valeric
acid.
[0012] One problem with using butyrates is the potent smell of
butyric acid during processing. However, once surplus of butyric
acid is removed from the plasticiser, the smell is reduced. It has
also been found that a PVC plastisol comprising polyol butyrates
according to the invention did not produce any unpleasant smell
under normal conditions. We have quite surprisingly found that a
pentaerythritol ester having one, two or three groups of butyrate
while the remaining groups are valerate indeed did smell much less
than expected during processing.
[0013] It is, according to one embodiment of the invention,
possible to esterify in two steps, first adding and reacting the
butyric acid with pentaerythritol in the desired molar ratio of the
finished product and in a second step add the valeric acid in
surplus. This way any smell from non-reacted butric acid will be
minimised.
[0014] It has, during experimentation with the plasticisers
according to the invention been found that the fusion time is very
short, while quite surprisingly, the volatility is still in parity
and in some cases lower than commercially available plasticisers.
The short fusion time implies that the processing time and/or
temperature during agglomeration of plasticiser can be lower
wherein the problem with smell during processing becomes even less
significant.
[0015] Tests were also performed with trimethylolpropane
trivalerate (TMP-V) which showed to be very volatile. A common
problem with volatility of plasticisers not many are aware of is
fogging on windshields in cars. The dashboard often becomes hot,
causing the plasticiser to evaporate and set as a film on the
inside of the windshield. This film is often rather difficult to
remove and will, with time, become a traffic hazard due to impaired
visibility, especially in low light conditions and when the sun is
close to horizon. It has shown that TMP-V does have very limited
use due to its volatility.
[0016] The present invention further refers to the use of said
plasticiser in a PVC resin. Pentaerythritol adipate can preferably
be used as a co-stabiliser in such a resin.
[0017] According to a special embodiment of the invention, a
plasticiser blend comprising 1-20 parts by weight of a plasticiser
being an ester formed by reaction of pentaerythritol and a
monocarboxylic acid being butyric or valeric acid which is blended
with 1-20 parts by weight of an oligo ester of 2-ethylhexanol and
furandicarboxylic acid. The plasticiser blend suitably comprises
1-5 parts by weight of the pentaerythritol ester blended with 1-5
parts of the oligo ester of 2-ethylhexanol and furandicarboxylic
acid. Preferably the plasticiser blend comprises 1-2 parts by
weight of the pentaerythritol ester blended with 1-2 parts by
weight of the oligo ester of 2-ethylhexanol and furandicarboxylic
acid.
[0018] The present invention is further explained with reference to
enclosed embodiment Examples, which are to be construed as
illustrative and not limiting in any way.
[0019] Example 1a illustrates the preparation of an ester of the
present invention: pentaerythritol tetra n-butyrate.
[0020] Example 1b illustrates the preparation of an ester of the
present invention: pentaerythritol tetra i-butyrate.
[0021] Example 1c illustrates the preparation of an ester of the
present invention: pentaerythritol tri n-butyrate,
mono-valerate.
[0022] Example 1d illustrates the preparation of an ester of the
present invention: pentaerythritol di n-butyrate, di-valerate.
[0023] Example 2 illustrates the preparation of an ester of the
present invention: pentaerythritol tetravalerate.
[0024] Example 3a illustrates the preparation of an ester according
to a special embodiment of the present invention: DOFDCA.
[0025] Example 3b illustrates the preparation of a plasticiser
blend according to a special embodiment of the present invention:
pentaerythritol tetra n-butyrate and DOFDCA.
[0026] Example 4 illustrates the preparation of plasticised PVC
sheets.
[0027] Example 5 illustrates the evaluation of obtained plasticised
PVC sheets.
EXAMPLE 1A
Synthesis of Pentaerythritol Tetra n-Butyrate
[0028] 2 mole of monopentaerythritol and 8 mole (+25% surplus) of
n-butyric acid were charged into a glass reactor equipped with
stirrer, condenser, nitrogen inlet and thermometer. 4% by weight of
xylene was added as an azeotropic solvent. The mixture was heated
under stirring to 220.degree. C. Esterification water began to
evaporate and when approximately 80% of a theoretical water amount
had been collected the reaction mixture was cooled to 150.degree.
C. and 0.1% by weight of titanium(IV)isopropoxid (Tyzor TPT) was
added as a catalyst. The mixture was subsequently heated to
220.degree. C. and maintained until a desired acid number was
reached and a theoretical water amount was collected, where after
the reaction mixture was cooled and the solvent and unreacted
n-butyric acid was removed under vacuum while slowly increasing the
temperature to 180.degree. C. After cooling, the solution was
neutralised by addition of calcium hydroxide and a small amount of
water, followed by vacuum distillation at 140.degree. C. and
filtration at room temperature. Pentaerythritol butyrate with 94%
tetra esterification was obtained.
EXAMPLE 1b
Synthesis of Pentaerythritol Tetra i-Butyrate
[0029] The synthesis where performed as in example 1a with the
difference that n-butyric acid was replaced by i-butyric acid.
EXAMPLE 1c
Synthesis of Pentaerythritol 1 Tri n-Butyrate Mono-Valerate
[0030] The synthesis where performed as in example 1a with the
difference that 6 mole of n-butyric acid and 2 mole of valeric acid
were blended before being charged into the glass reactor.
EXAMPLE 1d
Synthesis of Pentaerythritol Di n-Butyrate Di-Valerate
[0031] The synthesis where performed as in example 1a with the
difference that 4 mole of n-butyric acid and 4 mole of valeric acid
were blended before being charged into the glass reactor.
EXAMPLE 2
Synthesis of Pentaerythritol Tetravalerate
[0032] 2 mole of monopentaerythritol and 8 mole (+25% surplus) of
valeric acid were charged into a glass reactor equipped with
stirrer, condenser, nitrogen inlet and thermometer. 4% by weight of
xylene was added as an azeotropic solvent. The mixture was heated
under stirring to 220.degree. C. Esterification water began to
evaporate and when approximately 80% of a theoretical water amount
had been collected the reaction mixture was cooled to 150.degree.
C. and 0.1% by weight of titanium(IV)isopropoxid (Tyzor TPT) was
added as a catalyst. The mixture was subsequently heated to
220.degree. C. and maintained until a desired acid number was
reached and a theoretical water amount was collected, where after
the reaction mixture was cooled and the solvent and unreacted
valeric acid was removed under vacuum while slowly increasing the
temperature to 180.degree. C. After cooling, the solution was
neutralised by addition of calcium hydroxide and a small amount of
water, followed by vacuum distillation at 140.degree. C. and
filtration at room temperature. Pentaerythritol valerate with 97%
tetra esterification was obtained.
EXAMPLE 3a
Synthesis of DOFDCA According to a Special Embodiment of the
Invention
[0033] In a 700 ml round bottom glass flask equipped with an
agitator, condenser, Dean-Stark separator and inert gas inlet, was
charged 125 g of 2-ethylhexanol, 50 g of furandicarboxylic acid
(FDCA) and 0.07 g of tetraisopropyltitanate as catalyst. The
reaction mixture was during 150 minutes heated to reflux at
195.degree. C. The temperature was slowly increased to 215.degree.
C. while maintaining a good reflux. When the acid number was 0.3 mg
KOH/g the solution was cooled, vacuum applied and excess of
2-ethylhexanol distilled off Subsequently a small portion of water
was added, when the temperature was below 100.degree. C., to
destroy the catalyst. The reaction product was neutralised using a
base in excess to residual acid value. Vacuum was once more applied
and residual volatile compounds were distilled off at 150.degree.
C. during one hour. The reaction product, an oligoester
plasticiser, was finally cooled to room temperature.
TABLE-US-00001 Diester content, %: 99.5 Monoester content, %: 0.2
2-Ethylhexanol content, %: 0.02 FDCA content, % <0.02 Acid
value, mg KOH/g: 0.04 Viscosity at 20.degree. C., mPas 103 Colour,
Hazen: 360
Alternative Embodiment Ester
[0034] In a 700 ml round bottom glass flask equipped with an
agitator, condenser, Dean-Stark separator and inert gas inlet, was
charged 170 g of 2-ethylhexanoic acid, 50 g of
di(hydroxymethyl)furan, 7 g of xylene as azeotropic solvent and
0.07 g of tetraisopropyltitanate as catalyst. The solution was
during 150 minutes heated to reflux. The temperature was
subsequently slowly increased to 230.degree. C. while maintaining a
good reflux. The reaction product was, when the hydroxyl number was
less than 1 mg KOH/g was reached, cooled and vacuum was applied for
evaporation of excess 2-ethylhexanoic acid and xylene. A small
portion of water was added when the temperature was below
100.degree. C. to destroy the catalyst. The reaction product was
neutralised with a base used in an excess to residual acid number.
Vacuum was applied and residual volatile compounds were during one
hour distilled off at 150.degree. C. Yielded product, an oligoester
of plasticiser type, was finally filtered. The oligoester
plasticiser was by analysis determined to have a diester content of
more than 99%.
[0035] The plasticiser (DOFDCA) obtained in Example 3a was
evaluated in a PVC composition and compared to the commercially
available plasticisers, di-(2-ethylhexyl)phthalate (DOP),
di-(2-propylheptyl)phthalate (DPHP), di-(isododecyl)phthalate
(DIDP), di-(isononyl)phthalate (DINP) and
di-(isononyl)cyclohexanoate (DINCH).
TABLE-US-00002 The PVC composition was: PVC K-70 (Norvinyl S7060)
100 phr Plasticiser 50 phr Stabiliser Mark CZ 118E 2 phr
[0036] i) The fusion time was evaluated and found to be superior
for DOFDCA over the comparative plasticizers, implying improved
productivity for the PVC converter. The result is given in Graph 1
below. [0037] ii) The hardness was measured as ShoreA hardness
according to ASTM D 2240-3 after 1, 7 and 14 days at room
temperature and 50% relative humidity. The results below indicate
that DOFDCA is the most efficient plasticiser. The result is given
in Graph 2 below.
EXAMPLE 3b
Preparation of a Plasticiser Blend According to a Special
Embodiment of the Present Invention
[0038] 1 part per weight of pentaerythritol tetra n-butyrate from
example 1a where mixed with 1 part per weight of DOFDCA from
example 3a. The mix between pentaerythritol tetra n-butyrate and
DOFDCA was fully miscible.
COMPARATIVE EXAMPLE
TMP-V
Synthesis of Trimethylolpropane Trivalerate
[0039] 2 mole of trimethylolpropane and 6 mole of valeric acid were
charged into a glass reactor equipped with stirrer, condenser,
nitrogen inlet and thermometer. 4% by weight of heptane and 0.1% of
p-toluenesulphonic acid was added as an azeotropic solvent and
catalyst respectively. The mixture was heated under stirring to
140.degree. C. Esterification water began to evaporate at
125.degree. C. The temperature was increased to 180.degree. C. in
steps until all expected water had evaporated. The reaction was
followed until a desired acid number was reached and a theoretical
water amount was collected, where after the reaction mixture was
cooled and the solvent and unreacted acid was removed under vacuum.
The solution was neutralised by addition of calcium hydroxide.
Cellite was added and the product was then filtered.
Trimethylolpropane trivalerate with 95.7% tri esterification was
obtained.
EXAMPLE 4
Preparation of Plasticised PVC Sheets
[0040] PVC resins (suspensions of PVC particles in a plasticiser)
of below formulations were prepared:
TABLE-US-00003 PVC (Norvinyl S-706) (g) 190.8 190.8 190.8 190.8
190.8 190.8 Polyolester plasticiser from 95.4 -- -- -- -- --
Example 1a, P-nB (g) Polyolester plasticiser from -- 95.4 -- -- --
-- Example 1b, P-iB (g) Polyolester plasticiser from -- -- 95.4 --
-- -- Example 1c, (1:3:1) P-nB-V (g) Polyolester plasticiser from
-- -- -- 95.4 -- -- Example 1d, (1:2:2) P-nB-V (g) Polyolester
plasticiser from -- -- -- -- 95.4 -- Example 2, P-V (g) Plasticiser
blend from example -- -- -- -- -- 95.4 3b, (1:1) DOFDCA/P-nB
Stabiliser 3.8 3.8 3.8 3.8 3.8 3.8 (Mark CZ 118 E) (g) PVC
(Norvinyl, S-706) (g) 190.8 190.8 190.8 190.8 190.8 Plasticiser 1
(DPHP) (g) 95.4 -- -- -- -- Plasticiser 2 (DOP) (g) -- 95.4 -- --
-- Plasticiser 4 (DINCH) (g) -- -- 95.4 -- -- Plasticiser 3 (DINP)
(g) -- -- -- 95.4 -- Polyolester plasticiser from -- -- -- -- 95.4
comparative example, TMP-V (g) Stabiliser 3.8 3.8 3.8 3.8 3.8 (Mark
CZ 118 E) (g)
[0041] The components of each PVC resin were carefully mixed and
then calendered to a sheet using a two-roll mill at 165.degree.
C.
EXAMPLE 5
Evaluation of the Obtained Plasticised PVC Sheets
[0042] All plasticised PVC sheets obtained in Example 4 were
evaluated regarding fusion time, hardness, migration, volatility
and extraction/absorption in water, heptane and 1% soap solution
and yellowness.
Fusion Time
[0043] A test to determine the time required for PVC and
plasticiser to completely mix together and form a uniform blend. A
mixing bowl was heated to the test temperature of 88.degree. C. and
charged with 300 g PVC resin. A stirring of 60 rpm was applied for
5 minutes to allow the resin to reach the bowl temperature. 150 g
plasticizer was then added and the time required for PVC and
plasticiser to completely mix together and form a uniform blend was
measured.
[0044] The results are presented in Chart 1.
Hardness
Durometer Hardness Shore A. (Standard: ASTM 2240:3)
[0045] A test based on the penetration of a specific type of
indentor when forced into the material under specific conditions.
The indentation hardness is inversely related to the penetration
and dependant on the elastic modulus and viscoelastic behaviour of
the material.
[0046] The results are presented in Chart 2.
Migration
Determination of Migration of Plasticisers (Standard: ISO 177)
[0047] A test based on quantitative determination of the loss of
mass of a sheet of plasticized plastic placed between two fresh
absorbent backing discs. A rubber-PVC-rubber sandwich was wrapped
with aluminium foil and rubber sheets before being placed between
two glass plates. A weight of 5 kg was placed on the sandwich
assembly and the whole package was placed in an oven with a
temperature of 70.+-.2.degree. C. The samples were then picked out
and the weight of both the plasticized plastic and the absorbent
backing discs was measured after 3, 7, 14 and 28 days.
The results for 28 days are presented in Chart 3.
Volatility
Activated Carbon Method (Standard: ISO 176 Method A)
[0048] A test method based on quantitative determination of the
loss of plasticiser from plasticized plastic materials upon
heating, where it is generally assumed that no significant amounts
of other volatile materials are present. 120 cm.sup.3 of activated
carbon was spread on the bottom of metal container and a test
sample was placed on top of the carbon and covered with another 120
cm.sup.3 of activated carbon. Two further samples were placed in
the container, each covered with 120 cm.sup.3 of carbon, where
after the container was sealed with a lid. The container was placed
in oven with a temperature of 100.+-.1.degree. C. The activated
carbon surrounding the samples absorbed the plasticiser extracted
upon heating. After 7 days the container was removed from the oven
and cooled to room temperature. The samples were removed from the
container, carefully brushed free from carbon particles and
weighed.
[0049] The results are presented in Chart 4.
Absorption and Extraction
Determination of Absorption and Extraction of Water, Heptanes and
1% Soap.
[0050] A test method based on quantitative determination of the
loss of mass of plasticized plastic sheet completely immersed in
the test liquid for a specified time and at specified temperature.
The weight of the plasticized plastic sheets was determined before
immersion, after removal from the liquid and after drying. The
samples were immersed for 1 day in water and 1% soap solution at
70.degree. C. The samples were also immersed in heptane for 1 day
at 23.degree. C. The extracted samples were wiped dry, where after
the mass loss was determined.
[0051] The results are presented in Chart 5-7.
Yellowness
[0052] The yellowness observed during the test period (40 min) was
significantly lower in the PVC sheets plasticised with the
polyolesters from Example 1 and 2 compared to the PVC sheets
plasticised with DINCH, DOP, DPHP and DINP.
[0053] DPHP-1, DOP-2, DINP-3, DINCH-4
[0054] The fusion time for the plasticisers according to the
present invention was found to be shorter in comparison to certain
commercially available plasticisers 1-4.
[0055] The plasticising effect of the plasticisers according to the
present invention was found to be high in comparison to
commercially available plasticisers 1-4. This means that lower
amounts of plasticiser can be added with maintained hardness.
[0056] Especially the plasticisers P-iB and P-V according to the
invention showed very good migration values. The comparative
example, TMP-V showed to be poor due to its high migration
value.
[0057] Especially the plasticiser P-V according to the invention
showed very good volatility value. The comparative example TMP-V
showed to be poor due to its high volatility.
* * * * *