CA1054625A - Polyesters - Google Patents

Abstract

Abstract of the Disclosure Polyesters having an average molecular weight from 500 to 1400, containing dicarboxylic acid-, aliphatic diol- and hydroxy acid or lactone residues and which are endstopped by monohydric alcohols are useful plasticizers for example for PVC.

Description

5~ 5 The present invention relates to novel pl~sticisers for thermoplastic polymers such as polyvinyl chloride, and more particularly to plasticisers derived from alcohol end-stopped polyesters incorporating a lactone as co-reactant.
In British Patent Specification No. 1,289,516 there , is claimed a process for the preparation of a substantially primary hydroxyl-terminated linear or branched polyester ~` - which has a maximum true melting point of 30C containing l ~rom 25% by weight to 70% by weight of the epsilon -' oxycaproyl unit T -O(CH2)5-C-] comprising reacting material ~ which will provide the epsilon-oxycaproyl unit with at least ..
one dicarboxylic acid or its corresponding anhydride and at 5~ least two straight chain glycols of the formuIa HO(CH2)nOH
where n is an integer of 2 to 59 the proportions of the reactants being such that the resultant polyester has the `
~:~ required content of epsilon-oxycaproyl units. The polyesters 5~ ` thus produced after acylation are stated to be suitable for . -~
use as plastlcisers for vinyl resins.
In British Patent Specification No. 1,137,882 there i9 claimed a process for the manufacture of polyesters which : comprises reacting a mixture of the. following components:
(a) between 10 mole % and 65 mole % of ~-caprolactone, .
(b) between 45 mole % and 17.5 mole % of an aliphatic di- - :
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h~droxy compound, or of a mixture of two or more such compounds, and (c) between 45 mole % and 17.5 mole ~/0 of an aliphatic dicarboxylic acid, or of a mixture of two or more such acids, or of a mixture of one or more such acids -:
, 5 with a proportion not exceeding Io mole % of the total ;
acids used of an aromatic dicarboxylic acid, the proportions :
of the components (a), (b) and (c) of the reaction mixture !
being further selected, within the limi~s defined above, 3 according to the nature of the individual compounds consti-tuting components (b) and (c) in such a way that the overall ~ ratio of carbon to oxygen atoms in the polyester obtained ll excluding from consideration the oxygen atoms present in the - terminal groups, is at least 4.5:2, provided that when compo~
nent (b) consists of a single aliphatic ,~-dihydroxy compound and component (c) consists of a single aliphatic a,~ -dicarbo- . ~
xylic acid, at least one of components (b) and (c) is a ~ :
compound in which the main chain carbon atoms carry one or ~;.
more substituent groups which are lower alkyl groups having :
; from 1 to 4 carbon atoms. The polyesters thus produced are . 20 stated to be useful as plasticisers for vinyl chloride ! resins.
. British Patent Specification No. 859,642 describes ~ .
polyesters derived from lactones with at least one terminal .~
hydroxyl group as being useful as plasticisers for vinyl ~ ~.

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~5~6~5 halide and other resins. The polymerisation is initiated by such compounds as primary alcohols, diols containing from 2 to 10 carbon atoms and dicarboxylic acids such as phthalic acid, isophthalic acid and tereph~halic acid.
It is also stated that when the polyesters are to be used as plasticisers, the molecular weight may range between about 1500 and about 9000 and that optimum plasticising character-` ist;cs are obtained with polyesters having molecular weights :
between about 2000 and about 4000.
Surprisingly, we have found that a group of alcohol terminated polyesters having a molecular weight o 500 to l400 incorporating a lactone as co-reactant with an aromatic, or a partially or fully hydrogenated aromatic dicarboxylic acid and an aliphatic diol are valuable plasticisers for polyvinyl chloride which have improved efficiency when compared with plasticisers from similar reactants of higher molecular weight described in BY. 859,642 and improved ease of processing and other valuable properties when compared with other commercially available polyester plasticisers.
; 20 The molecular weight of the polyesters described in the ~;
.
present invention is determined by two factors: ~-' 1) the ratio number of moles of alcohol reactant number of moles of diol reactant R
. :
`i - 2) the mole ~/0 of the lactone used = C
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Decreasing R for a given value of C, increases the molecular weight and vice versa Increasing C for a ~iven value of R increases the molecular weight and vice Yersa According to the present invention there is provided a compound having the formula~
A~P)a(D)b~L)CA

; in which A is ~he residue of one or more saturated s~raight ~ :

or branched chain monohydric alcohols containing from l to ..
20 carbon atoms, P is the residue of one or more saturated g straight or branched chain aliphatic diols containing fro~
2 to 6 carbon atoms, D is the residue of one or more benzene ;~
g dicarboxylic acids which may be partially or fully hydro~
generate~ L is the residue of one or more saturated acyclic hydroxy acids containing from 4 to 14 carbon atoms, each of .; ~ .
the residues béing joined together by ester linkages~
residues P, D and L being distributed at random throughout .-~
the molecule, a, b and c each having a value greater tha~
O, the a~ount of residue of hydroxy acid being fro~ 10 mole %
to 90 ~ole ~ based on the total num~er of ~oles of reactants and the ratio of the number o lcs of alcohol to the number of moles of diol being from 2.2 to 0.93 such that the average molecular weight is from 500 to 1400. Liquid polyesters are ~ ~ :
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preferred since on the commercial scale they are much easier to handle and process than solid polyesters. ~ ;~
The average molecular weight is preferably from '~ 600 to 1000. The residue of the hydroxy-acid is preferably derived from the corresponding lactone, but could be derived' from the hydroxy-acid itself.
" The alcohol corresponding to residue A may be methanol, ethanol, n-butanol, isobutyl alcohol, n-hexanol, isooctyl alcohol, nonanol, isodecyl alcohol, mixed C12 and C13 normal alcohols (Dobanol 23), tridecanol, tetradecanol, octadecanol, eicosol, or a mixture thereof. Preferably, ; '~
c~ component A contains from 4 to 15 carbon atoms, especially ~ `
7 to 11 carbon atoms. Examples o~ the latter are isooctyl alcohol (a commercially available mixture containing branched , .~ " .
chain primary alcohols with eight carbon atoms), "Alphanol" 79 i (which consists mainly of straight- and branched-chain primary '~
'~ ~ alcohols containing 7-9 carbon atoms)~ 2-ethylhexanol, iso- ~-'1 decyl alcohol, Alfol 810 ~a commercial product consisting ~; ~ mainly of n-octanol and n-decanol), the mixtures of pre~
'I~ 20 ~ dominantly straight chain alipha~ic alcohols containing ~;'' ~ . ; , ~ 7 to 9 carbon atoms sold under the Trade Mark "Linevol" 79 ','~ and the mixture of predominantly straight chain aliphatic ,! ~ alcohols containing 9 to 11 carbon atoms sold under the Trade Mark "Linevol" 911. ~' 6 `;
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The diol corresponding to residue P preferably - ~.
contains from 2 to.4 carbon atoms.
The chain may, if desired, be interrupted by an oxygen atom as in diethylene glycol. Examples of these preferred diols are ethylene glycol; diethylene glycol;
. ~ propane-l, 2-diol; butane-l, 3-diol; 2,2-dimethylpropane-1, ~

3-diol; butane-l, 4-diol; pentane-l, 5-diol; hexane-l, 6-diol; -and di-propylene glycol, ~.:
. The dicarboxylic acid or anhydride corresponding to . 10 residue D may, if desired, be substituted with from 1 to 4 .
alkyl groups containing from 1 to 4 carbon atoms or with from ~:
1 to 4 halogen atoms such as chlorine or bromineO ~
The dicarboxylic acid or anhydride preferably contains ~;
Jl ' 8 carbon atoms and may be isophthalic acid, tetra-chloro- ;~
~15 ortho phthalic anhydride, but o-phthalic acid or phthalic .1 . .., anhydride is particularly preferred.
The lactone corresponding to residue L preferably ~ . contains 6 ring carbon atoms may, if desired, be substituted . ~:
,~ with one or more alkyl groups containing up to 4 carbon :20 atoms for example, methyl provided that the total number of carbon atoms does not exceed 12. Examples of lactones are ~-butyrolactone, zeta-enantholactone, eta-caprylolactone, j and lambdalaurolactone but -caprolactone itself is prefer-red.
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~C)5~25 When the lactone corresponding to the residue L is . epsilon-caprolactone and the ratio of the number of moles of alcohol to the number of moles of diol is 2.20, the amount : ;.
o -caprolactone is preferably 20 mole % to 70 mole %
"!
especially valuable polyesters being obtained when the amount of -caprolactone is from 30 mole % to 50 mole %:
when the alcohol to diol molar ratio approaches the lower l~nit of 0.93 the amount of - caprolactone is preferably 30 mole % to 50 mole %. :
The present invention also provides a process for :
the manufacture of polyesters of formula I which comprises :
~- reacting a mixture of the following components a) ~rom 10~ to 90 mole % of a lactone or hydroxy acid containing from ', 4 to 12 carbon atoms, b) from 22 to 2 mole % of a hydroxylic ~`~
~ 15 component which comprises one or more saturated straight ~-.~, or branched chain aliphatic diols containing from 2 to 6 I carbon atoms c) from 33 to 12 mole % of an acidic component ~
:l which comprises one or more aromatic or partially or fully ~:
hydrogenated aromatic dicarboxylic acids or anhydrides ~:~: 20 containing from 8 to 16 carbon atoms and d~ one or more :~`
1. ~ : saturated straight or branched chain monohydric alcohols ~:
;', containing from 1 to 20 carbon atoms such that the hydroxylic .
components are used in stoichiometric amounts or up to 15% ~ -excess over the stoichiometric amounts related to the acidic ~'" "":

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components.
. The amount of monohydric alcohol is ~referably from -. 93 to 220 mole % of the amount of the diol component, The process for the manufacture of the polyesters :~
of formula I may be carried out by conventional methods ~ .
; ~ " . , .` for the manufacture of polyesters prepared solely from ~-~
dihydroxy compounds and dicarboxylic acids.- For example .~ .the reaction mixture may conveniently be heated from 100C
`:! to 250C under conditions such that the water resulting ~-~
`~ 10 from the condensation reaction is removed as it is formed, for example by passing a current of inert gas through the :: heated reaction mixture or by conducting the reaction in -`
the presence of a suitable inert solvent such as xyLene, with which the water may be removed by distillation as an azeotrope, Preferably the reacti.on is continued until the ;~
proportion of carboxylic acid end groups in the resulting ~ :
: polyester corresponds to an acid value of not more than `~
10 milligrams and especially not more than 5 milligrams potassium hydroxide per gram.
~ 20~ ; I deslred a catalyst commonly used in polyester `!: ~ formation:may be~added to the reaction mixture for example :3~: strong acids BUCh as sulphuric acid, phosphoric acid, ;~
p-toluene sulphonic acid, Lewis acids such as stannic acid, l~ zinc chloride, aluminium chloride and metal salts and metal f - 9 ~
:f , ~,~ . ~ ' : :' ~05 .
; derivatives such as metal alkoxides for example tetrabutyl titanate, zinc adipate, antimony oxide and organo-tin compounds especially dibutyl tin oxide. The amount of catalyst used may be from 0.001% to 5% by weight based ~` 5 on the total weight of the reaction mixture. If desired ~
up to 1% by weight of activated carbon based on the total -., .
weight of the reaction mixture may be added either to the `~
reaction mixture or at the filtration stage to preserve the colour of the product. `
The polyesters of the present invention which may -be used in amounts up to 60% by weight of the plasticised composition are efficient, easily processed plasticisers with good extraction resistance. They show an improvement in permanence in PVC without loss of efficiency when compared with conventional non-polymeric plasticisers.
In fact, the polyesters of the present invention show a ~! remarkable combination of properties not present in con-ventional non-migratory plasticisers: not only to they possess resistance to extraction and migration but they overcome the major defect of plasticisers of this type ~. . , in being readily processed at temperatures commonly used ,l~ for monomeric plasticisers. The polyesters of the present , invention may be incorporated into thermoplastic polymers ', such as polyvinyl chloride or its copolymers by conventional i - 10 ~
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methods. If desired other conventional additives may be ,'3 present in the thermoplastic composition such as heat and -~ light stabilisers, antioxidants, fillers, pigments, lubri-cants~, processing aids, and other plasticisers.
Examples of heat and light stabilisers are as follows~
~ 1) Salts of inorganic or organic acids containing metals ;~ such as aluminium, barium, bismuth, calcium, cadmium, potassium, lithium, magnesium, sodium, lead, antimony, tin, strontium or zinc or any metal which is capabIe of - exerting a stabilising effect on PVC in salt form. The salts may be simple or complex.
'~ Examples of inorganic salts are basic lead carbo- -~
nate and tribasic lead sulphate.
Organic acids which may be used are.
a) Aliphatic carboxylic acids, straight or branched .:' ~ ; chain unsaturated or saturated, and optionally :3 : ~
containing hydroxyl substituents or oxygen in epoxy groups. Examples are zlnc 2-ethyl hexanoate, barium 20 ~ laurate and stannous octanoate. ~ ~ ~r-`~i b) Aromatic mono- or di-carbox~lic acids containing any ;~
~ type of substitution in the atomatic groups and any J~ ~ype of alkyl/aryl configuration.
~ Examples are cadmium p-tertiary butyl benzoate, ;~ , .

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calcium benzoate or lead salicylate.
c) As acidic materials, phenols capable of forming stable compounds (phenates) with metals whether in a suitable solution or not.
An example of such a compound is barium nonyl phenate.
2) Organo-metallic compound of any of the following metals, aluminium, barium, bismuth, calcium, cadmium, potassium, lithium, ma~nesium, sodium, lead, antimony, zinc, tin or strontium.
Examples of such compounds are dialkyl tinmercaptides and dialkyl tin carboxylates.
3~ Organic compounds of any description which prevent degradation of PVC. ~ ~ .
Among these are ~-phenyl ihdole or esters of amino crotonic acid.
All these compounds may be used alone or as mixtures with eacli other either as so]ids or as solutions in any suitable solvent not necessarily being a stabiliser.
~Combination which~may be used are of calcium~and zinc ;
- - ~ carboxylates or of a barium phenate with the cadmium salt of a branched chain fatty acid or of barium, cadmium and ¦ zinc carboxylates. ;
. .. .
,~ There may be used with the ~oregoing stabilisers, ;
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materials which enhance the effectiveness of the stabilisers but which are not stab;lisers for PVC when used als?ne, These are referred to as co-stabilisers and include a) Epoxidised oils and esters such as epoxidised soya bean oil or epoxidised octyl oleate b) Esters of phosphorous acid which may be trialkyl, ' triaryl, or alkyl-aryl~ For example triphenyl phos-~3 phite, tris (nonyl phenyl) phosphite or diphenyl isodecylphosphite.
c) Aliphatic hydrophilic compounds such as pentaery-, thritol, neopentyl, glycol, sorbitol or partial ~- esters o~ glycerol.
d) Phenolic compounds such as 2:6-di-tert-butyl 4-methyl ~-~
. ~ . .
~ phenol, or 2:2 bis (4'-hydroxy phenyl) propane.
:3i 15 These costabilisers can be used singly or together .;~i .
~ with the main stabiliser in any proportions and combinations.
`~ They may be applied in their natural state, alone or in ~ .
mixtures of stabilisers, or in solvent solutions, alone or ~ ~ in admixture with the stabilisers, using suitable solvents : 20 which are not necessarily PVC stabilisers.
.; . ~
I They may also be used in admixture with lubricants i ;? ` such as polyethylene waxes, ester waxes, stearic acid, calc-ium stearate, lead stearate, fillers such as calclum car-bonate ground or precipitated or china clays.

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They may also be used with materials which absorb ultra-violet light, making the PVC compound more stable to light exposure, for example benzophenones or benzo-., ~
triazoles.
They may also be used in admixture with other known plasticisers which may be:
a) Flame retardant such as triarylphosphates, alkyl di~
~, . aryl phosphates.
:~.i b) Phthalate esters c~ Low temperature plasticisers such as adipate, sebacate, j3 and azelate esters -:~
,~ ; . .:
i d) Conventional polyester plasticisers such as poly(l:3 ~ :
.. 1 -, . ~
butylene glycol adipate) end-stopped with a C8 alcohol . ~ or other typical members of this class.
;~: 15 e) Phenyl esters of alkane sulphonic acids -~
f) : Extenders comprising halogenated paraffins or :~
~; aromatic hydrocarbons. :~

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)54~Z5 ` The following Examples further illustrate the present invention.
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` Exam~les 1 to 6 , A 2 litre four necked round bottom flask-was fitted with a stirred in a ground glass stirrer gland, a 0-250C ~;
contact thermometer in a thermometer pocket, and a nitrogen inle~. The flask was also fitted with a vacuum jacketed ;~;
Vigreux column (6 inch effective length), surmounted by a water separator provided with a water-cooled condenser, The anhydride, ethylene glycol, isooctyl alcohol and ~' - -caprolactone in the amounts specified in Table I were ; , :~ ,' charged to the flask together with 10-15% by weight on the theoretical yield of polyester of xylene and 0.1% by ;~
weight based on the theoretical yield of polyester of dibutyl tin oxide in Examples 1, 2, 3, 5 and 6 and 1.$ grams hydroquinone in Example 4. Activated carbon in an amount 'I : ~, ; 1% by weight based on the theoretical yield of ester was added to the reaction mixture in order to preserve ~he colour o~ the product.
~ The reactants were then heated up to approximately~
200C over 8 hours with stirring, and this temperature main-tained for a further 10 hours. A slow stream~of nitrogen `-~
was passed into the reaction flask throughout the reaction.
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Water formed in the reaction was separated from the xylene in the water separator. When the acid value of the reaction mix~ure had reached the value given in Table 1, the solvent was removed by heating the reaction mass under reduced pressure. The m~ ture was finally vacuum stripped at 200C
for one hour at 20 millimetres mercury pressure. The product was filtered in a pressure filter under nitrogen and was ;~
obtained as a clear liquid. The yields and propertieis of ` these polyesters are given in Table 1.
.,' ` '~
` 10 Comparative Examples A and B
,~ Polyesters were prepared in a similar manner to that described in Examples 1 to 6 using dibutyl tin oxide as catalyst and using the amounts of reactants specified ~
in Table 1. The yields and properties of these polyesters -are given in Table 1.

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~`` lOS4~5 The viscosities of the polyesters of Comparative Examples ~.
~` A and B are so high that they are difficult to handle ` a process as plasticisers.
. . :
Examples 7 to 11 - 5 The compositions of Examples 7, 8, 9, 10 and 11 were obtained by incorporating 35 parts of the polyesters of i Examples 2, 3, 4, 5 and 6 respectively into 65 parts of `'1 polyvinyl chloride (Breon S 125/12), 4 parts of white ... ~ . . :: .
`~ ~ lead paste and 1 part calci~n stearate. The premix was ~-`j 10 compounded on a two roll mill at 165C for 15 minutes, and ~ - .
compression~moulded at 180C for 5 mlnutes. The physical properties are given in Table 2.
Comparative Examples C and D
The compositions of Comparative Examples C and D
15~ ~ were obtalned~by incorporating 35 parts of the polyesters of Comparative Examples A and B respectively into 65 parts of~polyvinyl chloride (Breon S125/12), 4 parts of white lead paste and I part calcium stearate. The premix was comp~ounded on a two roll mill at 165C for 15 mlnutes, and 20~ ~ ~ compression;moulded at 180C for 5 minutes. The physical ~
,;~properties are given in Table 2, ~ ~ `
~;The physical properties of the compositions of . ~Examples 7 to 11 and Comparative Examples C and D were '~5`~

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~:)5~Z5 . determined by the following methods.
~: a) International Rubber Hardness Degrees (IRHD) tested . . .
to BS 903 part A7 at 23C.
b) Extraction Resistance, The % weight loss from a ~
thin sheet (7.6 cm x 7.6.em x 0.018 cm) immersed ; ~:
; under the following conditi.ons:
PETROL - 75% iso-octane; 25% toluene; 1 hour at 23C
SO~P - 1% weight/volume solution of Lu~ flakes in distilled water; 24-hours at 60C.
After extraction the samples were dried for 1 hour :
~. ~ at 82.5C prior to reweighing, ,j~ c) Volatile Loss - The % weight loss on a sample 8 cm x 1 cm x 0.125 cm in 48 hours at 82.5C in a CIBA-GEIGY forced air oven.
d) Cold Flex (Clash & Berg) was determi.ned according to :, . .
BS 27~2 method 104B. .'~
e) .Clear Point - The temperature at which a few parti-. cles oX PVC heated in an excess of plasticiser and observed at a magnification of X 100 with a micro-scope are no longer discernible. The test indicates .
J~ the relative processability of formulations containing ; differing plasticisers. In general the lower the ~, clear point the easier the processing of the formulation.
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The polyesters of the present invention presented in th.e compositions of Examples 7 to 11 have good properties as PVC plasticisers with acceptable efficiency, good re- ~.
sistance to extraction and low volatile loss. In contrast :
the polyesters present in the conipositions of Comparative ~1 ' .
Examples C and D have very poor plasticisers efficiency as ~ ;~
shown by the IRHD of 99.5 and 99,7 respectively: these ;~:
polyesters are outside our inven-tion because the ratio mols alcohol is less than 0.93 but falls within those des-. mols diol :-. 10 cribed in B.P.859,642.
Moreover, the polyester present in the composition .: . . , :-of Comparative ~xample D which has a molecular weight ~:
,! falling within the preferred range described in B.P. 859,642 i is extremely inefficient since it was not possible to produce ~ ~
. 15 thin sheets of sufficient flexib:ility on which to carry out i`~.. :
extractions, % volatile loss and Clash and Berg tests. : :
Comparative Examples E, F, and G .
The clear points were measured of the polyester ;
: of Example 3 as well as of polyesters sold under~the Trade Names Plastolein 9506 (Unilever-Emery), Arbeflex 538 (Robinson Bros.) and Palamol 644 (BASF)~ The results are given in .
Table 3.

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~Q5~25 ~- TABLE 3 : .. __ .. __ _ . . .... .
~ EXAMPLE PLASTICISER CLEAR POINT
~ .... __ . .. __ .. _ :.~
Example 3 . 126C
.- E Plastolein 9506 144C ;
F Arbeflex 538 159C
. : G Palamol 644 155C :~
.~ . . _.____ . . . ._ _ .,:, ':
It should be noted that the large difference in ~ clear point shown between the plasticisers in Table 3 :', clearly demonstrates the superior processability of the : products of this invention. The unusually low value of Example 3 means that PVC compound can be made from this . plasticiser at lower temperatures and more quickly than '~ .
~ is possible with commonly used migration resistant com- ~
; ~~ mercial plasticisers.
~.: - ~ . ....

. : . ~ :-,,. ~

, : :.- ., ;~ :;'.~-~
- ': , ' ' - 22 ;. :

.

Claims (15)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A compound having the formula:

A(P)a(D)b(L)cA I

in which A is the residue of one or more saturated straight or branched chain monohydric alcohols containing from 1 to 20 carbon atoms, P is the residue of one or more saturated straight or branched chain aliphatic diols containing from 2 to 6 carbon atoms, D is the residue of one or more benzene-dicarboxylic acids which may be partially or fully hydrogenated, L is the residue of one or more saturated acyclic hydroxy acids containing from 4 to 14 carbon atoms, each of the residues being joined together by ester linkages, residues P, D
and L being distributed at random throughout the molecule, a, b and c each having a value greater than 0, the amount of residue of hydroxy acid being from 10 mole % to 90 mole % based on the total number of moles of reactants and the ratio of the number of moles of alcohol to the number of moles of diol being from 2.2 to 0.93 such that the average molecular weight is from 500 to 1400.

2. A compound according to claim 1 in which component A contains from 4 to 15 carbon atoms.

3. A compound according to claim 1 in which component A contains from 7 to 11 carbon atoms.

4. A compound according to claim 1 in which component A is the residue of isooctyl alcohol.

5. A compound according to claims 1 to 3 in which the diol corresponding to residue P contains from 2 to 4 carbon atoms.

6. A compound according to claims 1 to 3 in which the diol corresponding to residue P is ethylene glycol.

7. A compound according to claims 1 to 3 in which the dicarboxylic acid or anhydride corresponding to residue D contains 8 carbon atoms.

8. A compound according to claims 1 to 3 in which the residue D is derived from phthalic anhydride.

9. A compound according to claims 1 to 3 in which the residue L is derived from a lactone containing 6 ring carbon atoms.

10. A compound according to claim 1 in which the residue L is derived from epsilon caprolactone.

11. A compound according to claim 10 in which the amount of epsilon-caprolactone is from 20 mole % to 70 mole %.

12. A compound according to claim 10 in which the amount epsilon-caprolactone is from 30 mole % to 50 mole %.

13. A process for the manufacture of polyesters of formula I given in claim 1 in which A is the residue of one or more saturated straight or branched chain monohydric alcohols containing from 1 to 20 carbon atoms, P
is the residue of one or more saturated straight or branched chain aliphatic diols containing from 2 to 6 carbon atoms, D is the residue of one or more benzene-dicarboxlyic acids which may be partially or fully hydrogenated, L
is the residue of one or more saturated acyclic hydroxy acids containing from 4 to 14 carbon atoms, each of the residues being joined together by ester linkages, residues P, D and L being distributed at random throughout the molecule, a, b and c each having a value greater than 0, the amount of residue of hydroxy acid being from 10 mole % to 90 mole % based on the total number of moles of reactants and the ratio of the number of moles of alcohol to the number of moles of diol being from 2.2 to 0.93 such that the average molecular weight is from 500 to 1400 which comprises reacting a mixture of the following components a) from 10 to 90 mole % of a lactone or hydroxy acid containing from 4 to 12 carbon atoms b) from 22 to 2 mole % of a hydroxy-lic component which comprises one or more saturated straight or branched chain aliphatic diols containing from 2 to 6 carbon atoms c) from 33 to 12 mole %

of an acidic component which comprises one or more aromatic or partially or fully hydrogenated aromatic dicarboxylic acids or anhydrides containing from 8 to 16 carbon atoms and d) one or more saturated straight or branched chain monohydric alcohols containing from 1 to 20 carbon atoms such that the hydroxylic components are used in stoichiometric amounts or up to 15 % excess over the stoichiometric amounts related to the acidic components.

14. A composition comprising a thermoplastic polymer and a plasticising amount of a compound according to claim 1.

15. A composition according to claim 14, in which the thermoplastic polymer is polyvinyl chloride.