Title of Invention

A PROCESS FOR PREPARING A GELLED HYDRO CARBON COMPOSITION

Abstract The invention relates to gelled hydrocarbon compositions comprising a low molecular weight and a medium molecular weight triblock polymer. These gels can be used to make clear candles.
Full Text

The present invention relates to a prbcess for preparing a gelled hydrocarbon composition.
Candles of gelled hydrocarbon oils are well known, for example, as described in WO 96/34077 and WO 97/08282.
However, these gelled clear candles have the potential to catch fire since the difference between the pool temperature and flashpoint is smaller than in conventional wax candles. if the candle then ignites flames as high as 3 0 cms can occur with black smoke emanating. This is a potential health hazard and indeed is a reason why there have been a number of product recalls.
In addition it is important that the gelled candles do not flow when the candle holder is tipped on its side (e.g. as may occur during transportation or accidental spillage). Once the wick is buried in the gelled candle material, the product is spoiled.
In other words, such a candle material must be firm (i.e. not flow) and have large difference between the pool temperature and the flash point.
In the past it has been found that if for example the difference between the pool temperature and flash point is an acceptable amount, then there is too much flow, or vice versa. it has proved to be very difficult if not impossible to obtain an acceptable difference between pool temperature and flash point and at the same time produce a candle having desirable flow.

It is also well known in the art to use such gelled hydrocarbon oils for uses other than candles. For example, European Patent No.0224389 discloses styrene-dyene block copolymer compositions. However, none of these compositions would have suitable characteristics for forming candles.
International Patent Application No. W097/31623 discloses gelled compositions suitable for a wide range of uses, but not suitable for use in candles. This is particularly because the hydrocarbon used in the compositions disclosed in this international application are volatile and thus would be likely to present a severe fire hazard if used in candles. In addition, the material forming the candle would simply disappear with time, due to To alleviate these problems, there is provided a gelled hydrocarbon composition, suitable for use as a candle body, comprising a hydrocarbon oil gelled with a low molecular weight and a medium-moleculrax-weiqht triblock polymer.
By low molecular weight triblock polymer is preferably meant a triblock polymer of molecular weight (either Mw or Mn) from 20,000 to 82, 000, more preferably 50,000 to 82,000 most preferably; Mwis about 78,000_and Mn. is about 73,000_expressed as "polystyrene equivalent" molecular weights. An example of such a low molecular weight polymer is Kraton_G1652 (RTM).
By medium molecular weight triblock polymer is preferably meant a triblock polymer of molecular weight (either Mw or Mn) of from 82, 000 to 150, 000f more preferably 85,000 to 120,000,,, most preferably Mw is about


Preferably the molecular weight is measured by a technique known as wComparison of the molecular weight distributions of ethylene-butylene-styrene copolymers using wGel Permeation Chromatography", the process of which is as follows:
The determination of triblock polymers having low and medium molecular weight is expressed as the polystyrene equivalents. The samples are analysed using gel permeation techniques with tetrahydrofuran as the solvents and columns appropriate to low/medium molecular weight polymers.
It has been found that through careful selection of the low molecular weight and medium molecular weight triblock polymer, a candle having improved safety results.
In other words, through this careful selection, a candle may be formed in which the flash point and the pool temperature have acceptable values, and the difference between the pool temperature and the flash point is also large enough. Further, the resultant candle does not flow when the candle holder is tipped on it, s_sj.de.
A single solution of the sample is prepared by adding 10 mis of solvent to 20 mg of the sample and leaving for a minimum of four hours to dissolve. A small amount of 1,2-dichlorobenzene in the solvent is added as an internal marker and the solutions are mixed thoroughly. The solutions are filtered through a 0.2


Chromatographic conditions are as follows:
t
Columns PI gel 2X mixed bed D 30 cms, 5 microns Flow rate 1.0 ml/min Temperature 3 0C
Data acquisition and handling is carried out using Viscotek "Trisec 3.0" software. The GPC system was calibrated with polystyrene and the results are expressed as "polystyrene equivalent" molecular weight.
I The term «triblock polymer" is one well known in the art and suitable triblock polymers are styrene-&£Ml§ne/bm^^ne-styrene block copolymers such as are sold under the trade name KRATON G (RTM) by Shell. These copolymers are hydrogenated and"*" are thus thermally stable^_that is to say decomposition's not likely to occur during-the blending of the copolymer""*!th" the hydrocarbon oil. The KRATON G (RTM) copolymers are indicated as being compjy^^^j^^
naEthenic_oils and are reported as taking up more than 20 times their weight in oil to make a gelled product. Such co-polymers are described in WO 96/34077 and WO 97/08282. the contents of which are incorporated herein by ~ reference.
The triblock is often substantially pure triblock and may also include up to 5% diblock copolymer. Alternatively the triblock copolymers may contain blends with radial block copolymer or multiblock copolymer^ " Such copolymers and blends are described in WO 97/08282 and WO 97131623.

Desirable blends of low molecular weight and high molecular weight are in the ratios of 1 to 20 up to 20 to
^^—■ in- ■ mi iLIill— ■ —I* j i u. ,.j ■■-—
i^Preferably the blends are in the ratio of 1 to 10 up to 10 to 1, more preferably 1 to 5 up to 5 tcT~l
Both the low and medium molecular weight are tri-block co-polymers of the form a-b^a where b is an oil soluble^esic|]»i&*(e.g ethylene or butylene) and a an
^saitW4-i_*e;)'«>is'"-' ■ft"'-'-'"™- ' »^»,_...
insoluble styrene^jresidue^^ ~"
An example of this type of polymer is from the KratonjGJRTM) series of thermoplastic rubber polymers.
These polymers are a linear block.styrene-ethylene-butylene-styrene which have been hydrogenated to impart thermal stability during processing.
These tri-block polymers are supplied as >99% pure systems with either low1_jnedium or high molecular weights,.
These products can then be blended in the laboratory to change the rheological properties of the final hydrocarbon-oil gel as desired.
The hydrocarbon oil used is desirably a natural or synthetic hydrocarbon oil of C16 to C50, desirably as disclosed in WO 96/34077 or WO 97/08282. The oil may for example be a garaffinic oil, a naphthenic oil or a
«*-*,:■*..•„,/.:•• ml-.' .'-*••- "" - ■■ -I'- » l»-«l****wi*!r',«f'lifi-jeji.-» .!■.-[_«», .-.,.„
^turaljnlneraloil. The hydrocarbon oil can for example be a natural or synthetic cosmetic grade hydrocarbon oil. The hydrocarbon oil desirably is in liquid form at temperatures from 0° to 200° C. Preferred hydrocarbon oils are selected from paraffinic, oils naphthenic oils or natural mineral_oils, more preferably a white oil.


Preferably hjrcl^^ comprises a carbon chain
of 18 to 3 0 carbons n
The resistance to finw nf *-v,~ -in ^
——^^^±^^±^£±owot the gelled compositions
can be improved further by the addition of a small amount
(e.g^f^_i%! S*-A-*atty- aciflijBonomer e.g. a compound of formula I or formula II
HO - (CH2)U_ COOH (i)
CH3 -(CH2)p - CH(OH)- (CH2)q - COOH (II) in which u is 8 to 24
p is °-±oj.6, preferably 1 to 8, more
preferably i_to_.s and """"* "
S is .8 to 24( preferably 8 to 16, more preferably 8 to 10.
Desirably p and g is fr:onUL.to__24, preferably 12 tn 0, more preferably 14 to 18
A preferred fatty acid monomer is a stearic acid containing one or more hydroxy groups. A pl^tlc^^y preferred stearic acid is 12^ hydroxystearic_acid.
A gelled composition according to the invention will generally have an attractive clear appearance.
Further according to the invention, there is provided a candle comprising

i) a candle body and
ii) a wick located in the body,
said body comprising a gelled hydrocarbon composition comprising a hydrocarbon oil, gelled by polymerisation with a low molecular ^weight and medium molecular weight triblock polymer.
Still further according to the invention there is provided a process for preparing a gelled hydrocarbon composition comprising
i) mixing (e.g. homogenising) the said hydrocarbon oi_l_with the powdered trib^ock_copolymers at ei^Z§££dL temperature (e.g. 100 - 120° C) and
ii) optionally reducing the temperatureLof the above mixture (e.g. to about J70 - 90° C) adding, whilst mixing (e.g. at 400 - 500 rpm) fragrance to the above mixture.
The resulting mixture may then be homogenised at for example 4^„^„^5OO^^rgm.
The candle body desirably comprises the hydrocarbon oil in an amount of 70 to 99 wt%, preferably 85 to 95„ wt%, more preferably about 90 wt%.
Preferably the triblock polymers are present in an amount of 1-30 wt%, more preferably 5-15 wt%.
Preferably the fatty acid monomer if present is present in an amount of JQ^^^J3_jwt,%, more preferably 0.2 to 2 wt%, most preferably 0.5 to 1 wt%.

The candle body may comprise further components preferably 1 to 20% wt, such as one or more compounds selected from fragrances, malodour counteractants, insecticides, pesticides, insect repellants, colourants, anti-oxidants, preservatives, anti-ingestion agents, stabilisers, insect repellents, deodorizers and masking agents.
Suitable fragrances preferably 1- l0%wt are generally known in the art, for example one comprising fragrant materials selected from one or more of the following cedarwood^oil, sandalwood oil, bergamot, Bulgarian rose oil, patchouli, myrrh, clove leaf oil, linalol, ethyl alcohol, tepineol, menthol, citronellal and phenyl ethyl alcohol. The fragrance normally comprises a carrier solvent such as diethylphthalate, carbitol, dipropyleneglycol, or dipropyTgTy~coT7"~"
Suitable ^i^£^£^co^nterac^£nts are well known, for example is one or more aroma and/or non-aroma chemicals which are known to have an action in reducing the perception of the intensity of malodours for example unsaturated esters, ketones, aldehydes, and/or fraqrant materials such as citronellal or cedarwood oil (which is known to counteract the perceptionoftobacco malodour). Preferably JLJL^JLIwt .are present.
Suitable inseiSticiAes, pesticides- and in&ecjt
£ePei1^ants are wel1 known for use in the invention for example a pyrethroid,,.. .niotinoid, rqtenoid, tetramethrin, ^?allerthrin' allet]lirin, phenthrin,_dinitrophenol, organothiocyamate, benzene hexachloride, citronellal a polychlorinated cyclic hydrocarbon (for example heptachlor (RTM) , aldrin (RTM) or telodrin) or an organophosphorus compound for example tetraethyl pyrophosphate). Preferably l-iotrwt.is present.

Any Qfilourant used should be mi^s^luble. Examples of suitable colourants are Iragon Green (RTM), Iragon Violet (RTM) , Sandoplast Blue 2B and Fat Red 5B02. Preferably up to 2% wt is present.
A suitable anti-oxidant is, for example, tocopherol, ascorbyl palmitate, butylated toluene, ascorbic acid, tert-butyl hydroguinone, beta carotene, butylated hydroxy toluene or a gallate. Preferably 0.1 to 2% of an antioxidant may be present in the composition.
Suitable preservatives are quaternary alkyl ammonium compounds or imidazolinium derivatives. Preferably 0.1 to 2% of a preservative may be present in the composition.
An example of a suitable anti-ingestion agent is Bitrex (trade mark) which is made by McFarlane Smith Ltd and comprises denatonium benzoate. Preferably up to 2% wt of an anti-ingestion agents may be present in the composition.
A gelled composition according to the invention preferably comprises in addition to the hydrqcarbpn and the triblock copolymer,
i) JLcagxasce in an amount of up to 7wt%, preferably up
to 5 wt %,
ii) colouring agent in an amount of up to 1 wt% and
iii) antioxidant in an amount of up to 1 wt %.
All of the above percentages are in relation to the total weight of the candle body composition i.e. excluding the wick and container.

A candle body may be prepared by mixing the hydrocarbon oil and the medium molecular weight triblock copolymers and low molecular weight triblock copolymers at an ^IfivatedL^emBerature e.g. 120 - ipoc. a temperature of from ZQ__fcffi_SflLc, more preferably 80°C to 85°C. On cooling further the composition may then be added while the ml/pjolYmer ^ mix is still in liquid form. Preferably the components are mixed together and then poured into a container containing the wick to form the candle body.
Alternatively polymerisation of the gelled composition can be conducted in moulds or carried out to form a continuous or semi-continuous body which is then cut into the desired shapes. Preferably the polymerisation takes place when the wick is already present.
The invention will be illustrated by the following Examples.
Examples 1 to 6.
Method of Manufacture of the Candles from ttel
The candle consists of a liquid mineral oil that is gelled using a polymeric thickening agent e.g. a Kraton (RTM) co-polymer The candle may also contain fragrance and, if desired, a dye.
a) Method of manufacture of the gel
The appropriate amount of oil is weighed into a beaker and heated up to 120°C, whilst stirring with Heidolph nixer at 350-450 rpm.
tfhen the oil reaches 120°C co-polymeric thickening agent

e.g. the Kraton(s) (RTM) is/are gradually added whilst stirring.
When all the Kraton (RTM) has dissolved and the mix is reduced to about 85°C and fragrance and 12-hydroxystearic acid - if present is added slowly and left to stir for 10 minutes. Care is needed in adding the fragrance to the mix.
b) Method of manufacture of the r.anrll P>
The heater is turned off and a dab of gel mix is used to fix the wick to the base of the glass. The gel is then poured into candle glasses (lOOg fill weight).
The mix compositions are as set out below:











WE CLAIM:
1. A process for preparing a gelled hydrocarbon composition having a hydrocarbon oil and from 0.01 to 3% of a fatty acid said compound being gelled with a low molecular weight triblock polymer having a Mw or Mn from 20,000 to 82,000 and a medium molecular weight triblock polymer having a Mw or Mn of 82,000 to 1,00,000 comprising the steps of (i) homogenizing the said hydrocarbon oil with the powdered triblock
copolymers at a temperature of 100 to 120°C and (ii) reducing the temperature of the mixture obtained in step (i) to 70-90°C,
adding, while homogenizing at 400-500 rpm the fatty acid and fragrance
to the above mixture.
2. The process as claimed in claim 1, in which the triblock includes up to 5% diblock copolymer or contain blends with radial block copolymer or multiblock copolymer.
3. The process as claimed in any one of the preceding claims in which the triblock polymers are a linear block styrene-ethylene-butylene-styrene which is optionally hydrogenated to impart thermal stability during processing.
4. The process as claimed in any one of the preceding claims, in which the hydrocarbon oil is a natural or synthetic hydrocarbon oil of Ci6 to Cso, preferably a paraffinic oil, a naphthenic oil or a natural mineral oil.

5. The process as claimed in any one of the preceding claims wherein said fatty
acid is a compound of formula I or formula II

in which u is 8 to 24
p is 0 to 16, preferably 1 to 8, more preferably 3 to 5 and
q is 8 to 24, preferably 8 to 16, more preferably 8 to 10.
6. The process as claimed in any one of the preceding claims in which the hydrocarbon oil is present in an amount of 70 to 99 wt%, preferably 85 to 95 wt%, more preferably about 90 wt%, and the triblock polymers are present in an amount of 1-30 wt%, more preferably 5-15 wt%.
7. The process as claimed in any one of the preceding claims, wherein the gelled hydrocarbon compound comprises in addition to the hydrocarbon and the triblock copolymer,
i) fragrance in an amount of up to 7wt%, preferably up to 5 wt %, ii) colouring agent in an amount of up to 1 wt% and iii) antioxidant in an amount of up to 1 wt%.
8. A candle comprising
i) a candle body and
ii) a wick located in the body,
said body comprising a gelled hydrocarbon composition produced by the
process as claimed in any one of the preceding claims.

9. A candle as claimed in claim 8, in which the candle body comprises the
hydrocarbon oil in an amount of 70 to 99 wt%, preferably 85 to 95 wt%, more
preferably about 90 wt% and preferably the triblock polymers are present in an
amount of 1-30 wt%, more preferably 5-15 wt%.
10. A candle as claimed in claim 8 or 9, further including one or more components
(preferably in an amount of 1 to 20%wt), selected from fragrances, malodour
counteractants, insecticides, pesticides, insect repellants, colourants, anti
oxidants, preservatives, anti-ingestion agents, stabilizers, insect repellents,
deodorizers and masking agents.


Documents:

in-pct-2001-1401-che-abstract.pdf

in-pct-2001-1401-che-claims .pdf

in-pct-2001-1401-che-correspondance others.pdf

in-pct-2001-1401-che-correspondance po.pdf

in-pct-2001-1401-che-description complete.pdf

in-pct-2001-1401-che-form 1.pdf

in-pct-2001-1401-che-form 3.pdf

in-pct-2001-1401-che-form 5.pdf

in-pct-2001-1401-che-other documents.pdf

in-pct-2001-1401-che-pct.pdf


Patent Number 243776
Indian Patent Application Number IN/PCT/2001/1401/CHE
PG Journal Number 46/2010
Publication Date 12-Nov-2010
Grant Date 04-Nov-2010
Date of Filing 10-Oct-2001
Name of Patentee RECKITT BENCKISER (UK) LIMITED
Applicant Address 103-105 BATH ROAD , SLOUGH BERKSHIRE ,SL1 3UH ,UK
Inventors:
# Inventor's Name Inventor's Address
1 WILSON, SONIA ,KATHERINE HAMPTON TOWERS ,FLAT 5, SOUTHCOTE ROAD, READING RG30 2EW (GB)
PCT International Classification Number C11C 5/00
PCT International Application Number PCT/GB00/00879
PCT International Filing date 2000-03-10
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 9905558.4 1999-03-11 U.K.