Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – At least one aryl ring which is part of a fused or bridged...
Reexamination Certificate
2000-08-18
2004-05-11
Cheung, William (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
At least one aryl ring which is part of a fused or bridged...
C524S306000, C524S311000, C524S312000, C524S313000, C524S504000, C524S563000, C524S567000, C524S568000, C524S569000, C568S300000, C568S303000
Reexamination Certificate
active
06734241
ABSTRACT:
The manufacturing properties of thermoplastic polymers, for example the extruding properties of such polymers, is often modified/enhanced by the addition of plasticisers thereto. As acknowledged in the prior art, such as in U.S. Pat. No. 4,426,477, there is a tendency toward avoiding the commonly used plasticisers such as dioctyl adipate (DOA) and phthalate plasticisers such as dioctyl phthalate (DOP). The safety of these plasticisers has been called into question, particularly in certain applications.
U.S. Pat. No. 4,426,477 discloses plasticisers based on glycerol esters. The plasticisers consist of compounds prepared by the acylation of glycerol. The compounds comprises triesters, wherein approximately two of the acyls have two carbons and the remaining one acyl has from 10 to 14 carbons. The compounds of U.S. Pat. No. 4,426,477 provide a plasticising effect. However, in certain applications the plasticisers have a volatility such that they may migrate out of the thermoplastic polymer in which they are incorporated, such as PVC.
In a first aspect the present invention provides a composition comprising i) a thermoplastic polymer ii) a compound having the formula
wherein R
1
, R
2
and R
3
are independently selected from an acyl group or a hydrogen atom, wherein at least one of R
1
, R
2
and R
3
is an acyl group (a short acyl group) having from 2 to 6 carbon atoms, wherein at least one of R
1
, R
2
and R
3
is a branched chain acyl group (a long acyl group) consisting of or having a saturated chain having 10 to 20 carbon atoms and a hydrophilic branch group.
Preferably two of R
1
, R
2
and R
3
are short acyl groups as described above and the other of R
1
, R
2
and R
3
is a long acyl group as described above. In this aspect, the compound may be of the formula
Preferably the hydrophilic branch group is a group selected from acyl and derivatives thereof. Preferred derivatives include groups of the formula —O-acyl.
Preferably the hydrophilic branch group is a group of the formula
wherein p is from 0 to 4 or 0 to 3.
In a preferred aspect of the present invention the chain of the long acyl group consists of or has a saturated chain having 14 to 20 carbon atoms. In a more preferred aspect, the chain of the long acyl group consists of or has a saturated chain having 16 to 20 carbon atoms
Preferably the long acyl group is of the formula
wherein n is from 10 to 20 and m is 2n, and wherein p is from 0 to 4 or 0 to 3.
Preferably n is from 16 to 20, more preferably from 16 to 18, yet more preferably 17.
Preferably the group CnHm is a straight chain hydrocarbon group.
In a highly preferred aspect the long acyl group is a group of the formula
wherein x is from 7 to 10, preferably x is 10, and y is 2x, and wherein p is from 0 to 4 or 0 to 3, preferably p is 0.
Preferably the group CxHy is or comprises a straight chain hydrocarbon group.
In a highly preferred aspect the long acyl group is a group of the formula
In a preferred aspect of the present invention the short acyl group is or comprises an acyl group having from 2 to 5 carbon atoms. In a more preferred aspect, the short acyl group is or comprises an acyl group having 2 carbon atoms. The short acyl group is preferably of the formula
Preferably the short acyl group and the hydrophilic branch group contain the same number of carbon atoms. In a highly preferred aspect the hydrophilic branch group is a group of the formula
and the short acyl group is of the formula
wherein p=q and is from 0 to 4 or 0 to 3.
In certain aspects, it is desirable for the short acyl groups to be present in a maximum amount with respect to the total amount glycerol and esters thereof present in the composition. Preferably the short acyl group is present in an amount on average, of no greater than 2 moles per mole of glycerol and esters thereof present in the composition.
In certain aspects, it is desirable for the long acyl groups to be present in a minimum amount with respect to the total amount glycerol and esters thereof present in the composition. Preferably the long acyl group is present in an amount, on average, of at least 0.4 moles, preferably from 0.9 to 2 moles, more preferably from 0.9 to 1 moles per mole of glycerol and esters thereof present in the composition.
It may also be preferred for the majority of the glycerol present in the composition to be fully acylated Accordingly, in a preferred aspect the total amount of acyl groups is, on average, 2.7 to 3.0 moles per mole of glycerol and esters thereof
The compound of the present invention may be prepared by interesterification between glycerol and one or more oils, including natural oils and hardened natural oils followed by acylation. Thus, the compound of the present invention may be the product of a two part process comprising (i) an interesterification between glycerol and an oil selected from castor oil, including hardened castor oil, unhardened castor oil and mixtures thereof, and (ii) acylation.
Thus in a further aspect the present invention provides a process for the preparation of a compound having the formula
wherein R
1
, R
2
and R
3
are independently selected from an acyl group or a hydrogen atom; wherein at least one of R
1
, R
2
and R3 is an acyl group (a short acyl group) having from 2 to 6 carbon atoms or from 2 to 5 carbons; wherein at least one of R
1
, R
2
and R
3
is a branched chain acyl group (a long acyl group) consisting of or having a chain having 10 to 20 carbon atoms and a hydrophilic branch group; the process comprising the steps of:
(i) interesterification between glycerol and triglyceride compound having the formula
wherein each of R
1
, R
2
and R
3
is a fatty acid group consisting of or having a chain having 10 to 20 carbon atoms, to provide a composition comprising glycerol, monoglyceride, diglyceride and/or triglyceride;
(ii) optionally isolating the monoglyceride and/or diglyceride from the composition;
(iii) acylating the monoglyceride and/or diglyceride or the composition containing the same.
In the process of the present invention the chain having 10 to 20 carbon may be saturated or unsaturated.
The process of the present invention may utilise, for example, castor oil or hardened castor oil. The compound of the present invention may be prepared from hardened castor oil. A typical fatty acid profile of castor oil and hardened castor oil is given below.
Fatty Acid
Content [%]
Castor Oil
Palmitic (C16)
1.0
Stearic (C18)
1.1
Oleic (C18:1)
3.8
Linoleic (C18:2)
4.4
Linolenic (C18:3)
0.5
Gadoleic (C20:1)
0.5
Ricinoleic (C18:1-OH)
87.4
Hardened Castor Oil
Palmitic (C16)
1.3
Stearic (C18)
9.3
Oleic (C18:1)
0.9
Linoleic (C18:2)
0.2
Arachidic (C20)
0.7
Ricinoleic hard (C18-OH)
84.9
The nomenclature in parenthesis is Cxx:y where xx is the fatty acid carbon number and y indicates number of double bonds. Ricinoleic acid, hard (also known as 12-hydroxy stearic acid) has a hydroxyl group (OH) on the 12
th
carbon.
In this aspect the product based on the castor oil, or indeed a product based on another oil, may be synthesised as follows. These synthetic routes are given by way of example only. Other routes would be appreciated by a person skilled in the art
Route 1
Castor oil and glycerol are reacted to produce an equilibrium mixture of different glycerol esters. This mixture can be distilled and subsequently acetylated to provide the desired end products. This route is illustrated below.
The second, step comprising the removal of the glycerol followed by distillation is optional. In other word the mixture of glycerol, glycerol monoester, glycerol diester, and glycerol triester may directly acetylated with acetic anhydride to form a mixture of acetylated products. The acetylated monoglyceride or the mixture of acetylated products may have a yellowish color. The yellowish product may be distilled. The distilled product is clear.
Depending on the ratio between castor oil and glycerol and depending on the reaction conditions, the described process provides different glycerol ester mixtures. The glycerol monoester is typically 45-65% and may
Kristiansen Jorgen Kirk
Nielsen Bjarne
Sparso Flemming Vang
Cheung William
Danisco A/S.
Frommer Lawrence & Haug
Kowalski Thomas J.
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