GB1586505A - Creación de Inventos y Patentes con Inteligencia Artificial

GB1586505A – Polyester compositions
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GB1586505A – Polyester compositions
– Google Patents
Polyester compositions

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Publication number
GB1586505A

GB1586505A
GB36960/77A
GB3696077A
GB1586505A
GB 1586505 A
GB1586505 A
GB 1586505A
GB 36960/77 A
GB36960/77 A
GB 36960/77A
GB 3696077 A
GB3696077 A
GB 3696077A
GB 1586505 A
GB1586505 A
GB 1586505A
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Prior art keywords
acid
polyamide
molecular weight
poly
radicals
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1976-09-07
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GB36960/77A
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Uniqema BV

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Uniqema BV
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1976-09-07
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1977-09-05
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1981-03-18

1977-09-05
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Uniqema BV

1981-03-18
Publication of GB1586505A
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patent/GB1586505A/en

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Classifications

C—CHEMISTRY; METALLURGY

C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON

C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS

C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers

C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

C—CHEMISTRY; METALLURGY

C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON

C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS

C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers

Description

PATENT SPECIFICATION ( 11) 1 586 505
4 M ( 21) Application No 36960/77 ( 22) Filed 5 Sept 1977 ( 31) Convention Application No 720555 9 ( 32) Filed 7 Sept 1976 in = ( 33) United States of America (US) ( 44) Complete Specification published 18 March 1981 ( 51) INT CL 3 C 08 L 67/00 (C 08 L 67/00 77/06) ( 52) Index at acceptance C 3 R 3 C 3 N 1 C 13 M C 22 C 24 C 33 B C 4 C 6 X C 8 R L 6 D L 6 F M C 3 Y B 262 B 263 B 270 G 310 ( 54) POLYESTER COMPOSITIONS ( 71) We, UNILEVER-EMERY N V, a company organised under the laws of The Netherlands, of Buurtie 1, Goude, The Netherlands, do hereby declare the invention for which we pray that a patent may be granted to us and the method by which it is to be performed, to be particularly described in and by the following statement: 5
This invention relates to thermoplastic polyester and copolyester resin compositions.
Control of flow or rheological properties of thermoplastic polyesters during processing, such as extrusion, molding, milling and forming into fibers, is necessary The amount and type of additives employed for this purpose is 10 dependent on the particular polyester used, th 6 other compounding ingredients present in the formulation, the type of processing and the processing conditions.
Numerous additives for thermoplastic polyesters are known and used as flow promoters, friction reduces release agents, parting agents, spinning aids and the like For example, when processing polyester fibers ethoxylated fatty esters and 15 emulsified polyethylene, natural and synthetic waxes or mineral oils can be used.
Fatty amides or bisamides are also used as lubricating aids when polyesters are extruded Stearic acid, metal stearates, mono and dialkyphosphates and their metal soaps, and waxes such as carnauba and candellila, are also commonly used with polyesters in molding applications 20 We have now discovered polymeric additives capable of functioning as multipurpose processing aids for polyesters and copolyesters The SE polymeric additives can be readily incorporated into the polyesters and copolyesters, are compatible with other compounding ingredients typically employed, and do not detract from the desirable physical characteristics of the polymer Additionally, 25 these additives can be used at relatively high levels to impart other desirable properties to the polymer Even when used at high levels these polymeric additives do not exude or migrate from the polyester and form an undesirable sticky or oily residue on the surface of the manufactured article Also, in certain processing operations additional benefits are obtained For example, in extrusion applications 30 these additives permit the use of lower extrusion temperatures and less power while maintaining throughputs equivalent to the control.
These polymer additives are high melting polyamides derived from high molecular weight dibasic acids Polyamide resins of this type are known for adhesive applications and are commonly available, however, it is unexpected that 35 these polyamide resins can be advantageously used with polyesters and copolyesters to obtain improved thermoplastic compositions It is particularly surprising since the general practice throughout the industry has been to avoid the use of polyamides with polyesters since the presence of some free amine is inevitable and generally considered to be detrimental It is, in fact, surprising that 40 the polyamide additives are even compatible with the polyesters in view of the statements such as that found in the Encyclopedia of Polymer Science and
Technology, Vol 10, p 601, Interscience Publishers ( 1972) that fatty polyamides (condensation products of di and polyfunctional amines and di and polybasic acids obtained by the polymerization of unsaturated vegetable oils or their esters) 45 are generally incompatible with polyesters.
The polyamides according to this invention useful as additives for polyesters and copolyesters are high molecular weight products having a number average molecular weight from 5,000 to 50,000 and, more preferably from 10,000 to 35,000, obtained by the reaction of essentially stoichiometric amounts of a longchain, high 50 2 1,586,505 2 molecular weight aliphatic or cycloaliphatic dibasic acid containing from 18 to 52 carbon atoms, and optionally up to 30 weight percent of a short-chain saturated dibasic acid containing from 2 to 13 carbon atoms, with an aliphatic saturated diamine or mixture of diamines containing from 2 to 10 carbon atoms The polymeric additives typically have softening points in the range 100 to 240 C with 5 amine values less than 3 Especially useful additives are those polyamides derived from polymeric fatty acids obtained by the dimerization of predominantly C,8 acids, particularly polymeric fatty acid products containing 75 % by weight or more C 36 dimer acids, and mixed diamines differing in chain length by at least 3 carbon atoms and wherein the longer chain diamine constitutes from 5 to 35 equivalents 10 percent of the total diamine Even more preferable are those polymeric additives where azelaic acid, sebacic acid, dodecanedioic acid or brassylic acid are employed as part of the dibasic acid charge and the diamine used is a mixture of ethylenediamine and hexamethylenediamine The polymeric additives constitute 0 01 to 20 weight percent of the polyester or copolyester resin These additives are 15 especially useful with poly(ethylene terephthalate), poly(butylene terephthalate), and poly(l,4-cyclohexylenedimethylene terephthalate) resins and copolyesters thereof.
The present invention provides a process for improving the properties of thermoplastic polyester and copolyester resins which comprises incorporating 20 therein 0 01 % to 20 % by weight based on said resins, of a high molecular weight polyamide additive containing radicals of a high molecular weight aliphatic or cycloaliphatic dibasic acid containing from 18 to 52 carbon atoms and from 0 to 30 weight percent, based on the acid radicals, of a short-chain, saturated, aliphatic dibasic acid containing from 2 to 13 carbon atoms and 90-110 equivalent percent 25 radicals of ari aliphatic saturated diamine containing from 2 to 10 carbon atoms or a mixture of said diamines The enhanced flow characteristics of the resin also facilitate the production of molded goods:The polymeric additives of this invention are multipurpose and in addition to improving the processability of the resin by functioning as a lubricant and flow promoter during molding, milling, 30 extruding and fiber formation they also improve the properties of the resulting product, e g improve flexibility, improve flexural strength, improve impact resistance and the like It has also been found that by the use of these additives strains initially present in the molded pieces are relieved upon standing This feature is particularly useful in production of complex molded articles 35 The polyamides useful for this invention are high melting resinous products obtained by the reaction of a long-chain dibasic acid containing 18 or more carbon atoms and a diamine or mixture of diamines Some short-chain dibasic acids may also be present in the reaction The long-chain, high molecular weight dibasic acids used in the preparation of polyamide can be aliphatic or cycloaliphatic 40 hydrocarbon acids containing 18 to 52 carbon atoms The acids may be straightchain, i e, unbranched, or contain one or more alkyl branches and the carboxyl groups can be located in the terminal positions or randomly throughout the molecule Preferably the dibasic acids useful for this invention contain from 21 to 36 carbon atoms, or are mixtures thereof Some monobasic acids and/or polybasic 45 acids may be present with the dibasic acid, however, the dicarboxylic acid content should be at least 70 % by weight of the acid mixture and, more preferably, greater than 80 % by weight Dicarboxylic acids suitable for the preparation of the polyamides are obtainable by any of several processes known to the industry The dibasic acids can 50 be obtained from suitable organic compounds, for example, by ozonolysis of unsaturated carboxylic acids or the catalytic oxidation of saturated and/or unsaturated hydrocarbons They can also be obtained by oxidation of methyl or formyl-branched acids such as isostearic acid or formylstearic acid Carboxystearic acids such as heptadecane 1,3 dicarboxylic acid and heptadecane 1,9 55 dicarboxylic acid as well as other isomeric acids can be produced in this manner.
The radical addition of a short-chain aliphatic acid and unsaturated fatty acid also yields useful dibasic acids Dicarboxylic acids can also be obtained by the addition of acrylic acid or methacrylic acid and a monobasic acid containing conjugated unsaturation (e g linoleic acid) For example, when linoleic acid and acrylic acid 60 are reacted a dibasic acid of the formula L 586505 3 C 6-H 1 3 < 7}> C 7 H 4 C 00 } 1 2 (I COOII is obtained These adduct acids are very useful for the preparation of the polyamide resins employed for this invention.
Especially useful dicarboxylic acids for this invention are polymeric fatty acids obtained by the dimerization of unsaturated monocarboxylic acids containing 16 to 5 26 carbon atoms, such as oleic acid, linoleic acid, linolenic acid and eleostearic acid Dicarboxylic acids produced in this manner, that is, when two moles of unsaturated monocarboxylic acid are combined, are referred to as dimer acids.
Processes for the production of dimer acids are well known to the art and by way of illustration reference may be made to British Specifications Nos 825534, 825835 10 and 904343.
Dimer acids obtained by the dimerization of C 18 acids such as oleic acid, linoleic acid and mixtures thereof (e g tall oil fatty acids) are especially useful and advantageously employed for the preparation of the polyamide additives Such dimer acids have as their principal component C 36 dicarboxylic acid and typically 15 have an acid value in the range 180-215, saponification value in the range 190205 and neutral equivalent from 265-310 Dimer acids containing unsaturation may be hydrogenated prior to use Dimer acids containing less than 25 % by weight by-product acids, including monobasic acids, trimer acids or higher polymer acids, provide especially useful polyamide resins for this invention and it is particularly 20 advantageous if the C 36 polymeric acid has been hydrogenated and molecularly distilled or otherwise purified to increase the C 36 dimer content to 90 % or more.
Reacted with the long-chain, high molecular weight dibasic acid is in aliphatic diamine corresponding to the formula H 2 N-(-CH 2-),-NH 2 25 where N is an integer from 2 to about 10 and preferably from 2 to 6 Useful saturated aliphatic diamines of the above type include ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, octamethylenediamine and decamethylenediamine Mixtures of one or more of these diamines may be used, in fact, polyamides prepared from a 30 mixture of ethylenediamine and hexamethylenediamine form a preferred embodiment of this invention In addition to the above-mentioned saturated aliphatic diamines, which are essential if suitable polyamide additives are to be obtained, one or more additional diamines may also be used but should not constitute greater than 30 weight percent of the total diamine charge 35 Preferably such diamines will comprise less than 10 weight percent of the total diamine and include but-are not limited to the following: 3,4,5 trimethylhexamethylenediamine, dimer diamine (diamines of dimer acids obtained by the polymerization of oleic acid or similar unsaturated acids), p xylylenediamine, p phenylenediamine, 1 methyl 2,4 diaminobenzene, N,N’ dimethylphenyl 40 enediamine, 1,4 diaminocyclohexane, bis (p aminocyclohexyl)methane, N,N’ dimethyl 1,4 diaminocyclohexane, piperazine, 2,5 dimethylpiperazine, isophoronediamine, N oleyl 1,3 diaminopropane, N coco 1,3 propylenediamine and methylimino his propylamine.
In addition to the long-chain, high molecular weight dibasic acids, there may 45 1.586 505 A also be present and it is often advantageous to include a short-chain saturated aliphatic dibasic acid containing from 2 to 13 carbon atoms, and more preferably, from 6 to 13 carbon atoms The amount of the short-chain dibasic acids should not, however, exceed 30 weight percent of the total dibasic acid charge Useful shortchain acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic 5 acid, suberic acid, pimelic acid, azelaic acid, sebacic acid, dodecanedioic acid and brassylic acid.
Polyamides obtained by reaction of the above-described reactants and useful for this invention have number average molecular weights from 5,000 up to 50,000 and, more preferably, in the range 10,000 to 35,000 The polyamide resins have 10 softening points from about 1000 C to 2400 C, however, superior results are obtained when the softening point of the resin is in the range 1500-2100 C The polyamides must have amine values less than 20, preferably less than three, and preferably less than one, if they are to be useful as polymeric additives for polyesters Such resins are obtained by reacting essentially stoichiometric amounts (less than 10 o/% excess 15 of either reactant) of the diamine or mixture of diamines with the high molecular weight dibasic acid or mixture of high molecular weight and short-chain dibasic acids In other words a balanced or essentially balanced reaction is necessary and the reaction should be carried to completion or near completion, i e low amine value, preferably near zero 20 As indicated the equivalents ratio of the diamine (total) and dibasic acid (total) will be approximately 1:1 to obtain the polymeric additives The dicarboxylic acid charge may contain up to 30 weight percent of a saturated C 2,3 aliphatic dicarboxylic acid Preferably saturated aliphatic dibasic acids containing from 6 to 13 carbon atoms will be present in an amount from about 1 to 20 weight percent of 25 the total dibasic acid charge While a single diamine component may be employed for the preparation of the polymeric additive, a mixture of two diamines provides especially useful polyamides particularly when the diamines differ by at least three carbon atoms In such mixtures the longer chain diamine will constitute from 5 to 35 percent of the total diamine equivalents and, more preferably, from 10 to 30 30 equivalents percent The shorter chain diamine will make-up the remainder of the diamine charge Mixtures of ethylenediamine and 1,6 hexamethylenediamine have been found to be particularly advantageous and form a preferred embodiment of this invention especially when reacted in the above-defined ratios with a mixture of C 3, dimer acid and azelaic, sebacic, dodecanedioic or brassylic acids While 35 considerable compositional variation is possible with the polyamide additives the amount and type of the various dibasic acid and diamine components making up the charge are designed to provide a homogeneous product with the highest possible viscosity and melting point for that particular molecular weight.
The polyamides are obtained by heating the diamine and dicarboxylic acid 40 components in a suitable reactor arranged to permit water of condensation formed during the reaction to be removed from the system A variety of condenser/trap arrangements are acceptable for this purpose The reaction can be conducted as a batch, continuous or semi-continuous operation Reaction is achieved by heating the reaction mixture in the temperature range 150-280 C, preferably 180250 C, 45 until evolution of water ceases and a negative test for free amine is obtained.
Reaction times can vary from 4 to 24 hours depending on the particular reactants employed and the maximum reaction temperature More usually reaction times range from 6 to 10 hours An inert gas may be bubbled through the reaction mixture to facilitate removal of water During the latter stages of the reaction it 50 may be advantageous to reduce the pressure to remove the final traces of water At the end of the reaction the polyamide may be cooled and used as such or stabilizers, ultraviolet absorbers or the like added.
The polyamide additives are useful with a wide variety of polyesters and copolyesters and generally will be present in an amount ranging from 0 01 to 20 %, 55 and more preferably 0 1 to l O/ by weight based on the weight of the resin In general, the polyesters are obtained by the reaction of an aliphatic saturated glycol of the formula HO-(-CH 2-)2-OH where x is an integer from about 2 to 10 with a dicarboxylic acid or ester thereof, 60 preferably a C,4 alkyl ester Typical glycols include ethylene glycol, 1,3 propanediol, 1,4 butanediol, 1,6 hexanediol and 1,8 octanediol Cycloaliphatic diols such as 1,4 cyclohexanedimethanol can also be employed Terephthalic acid 1,586,505 1,586,505 5 and dimethyl terephthalate form especially useful polyesters particularly when the diol is ethylene glycol, 1,4 butanediol or 1,4 cyclohexanedimethanol While the polymeric additives are particularly effective processing aids for poly(ethylene terephthalate), poly(butylene terephthalate) and poly( 1 l,4 cyclohexylenedimethylene terephthalate) they are equally effective with copolyesters which 5 contain the elements of one or more additional reactants in minor proportions.
Such co-reactants can include other dicarboxylic acid components such as isophthalic acid, adipic acid, suberic acid, succinic acid, carbonic acid, oxalic acid, glutaric acid, fumaric acid, sebacic acid, azelaic acid, dimer acid and esters of these acids Brominated diols and brominated dicarboxylic acids, esters or anhydrides 10 and the ethoxylated derivatives thereof such as 2,5 dibromoterephthalic acid, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, chlorendic anhydride, brominated 1,4 butanediol, 2,2 bis(bromoethyl)propane 1,3 diol, 1,4 di( 2 hydroxyethoxy) 2,5 dibromobenzene, 2,2 bisl 3,5dibromo 4 ( 2 hydroxyethoxy)phenyllpropane, diethoxylated 3,5 dibromo 4 hydroxy 15 benzoic acid and the like are also advantageous The use of such brominated coreactants is particularly desirable when flame retardant copolyesters are desired.
To improve disperse dyeability of the copolyester small amounts of adipic acid or azelaic acid are often employed Sulfonated isophthalic acid can be reacted into the copolyester to improve the basic dyeing properties in textile applications 20 While numerous co-reactants can be employed for a variety of purposes the amount of said co-reactants will generally not exceed 10 mol percent of the copolyester and preferably will be less than 5 mol percent.
The polyamide additives of this invention can be incorporated into the resin using conventional processing equipment and do not require special mixing or 25 handling Furthermore, these additives are compatible with other known additives typically employed in thermoplastic polymer formulations such as stabilizers, lubricants, plasticizers, delusterants, dyes, pigments and antistatic agents The additives of this invention are also useful with filled resin compositions such as glass fiber or mineral filled polyesters 30 The polyamide processing aids of this invention also find application in blends of polyesters and copolyesters with other polymeric materials Polymers which can be blended with the polyesters and copolyesters include, for example, polyethylene, polypropylene, polyisobutylene and other polyolefins including copolymers and terpolymers such as copolymers of ethylene and butene 1 or 35 propylene and terpolymers of ethylene and propylene with diolefinic termonomers; ethylene-vinylacetate copolymers; butadiene-acrylonitrile copolymers and acrylonitrilebutadiene styrene terpolymers; poly(vinyl chloride) and poly(vinylidene chloride) homopolymers and copolymrers; polysulfones; polyacetal homopolymers and copolymers; polyphenylene ethers and silicone polymers 40 Additionally, the polymeric processing aids are useful with blends of two or more polyesters and/or copolyesters.
The following examples will illustrate the invention more fully In these examples all parts and percentages are given on a weight basis unless indicated otherwise Empol is a Registered Trade Mark 45 EXAMPLE I
A glass reactor equipped with a stirrer, nitrogen inlet, thermometer and condenser fitted with a water trap was charged with 0 242 equivalent dimer acid (Empoli R) 1010 dimer acid containing 97 o/ C 36 dibasic acid) and 0 161 equivalent azelaic acid Several drops 50 aqueous hypophosphorous acid were added and 50 the reaction mixture heated to 180-190 C with stirring:under a slight nitrogen flow A mixture of diamines consisting of 0 073 equivalent hexamethylenediamine and 0 322 equivalent ethylenediamine was slowly added over a period of about one hour while maintaining the temperature and removing water of condensation The reaction mixture was heated to about 230-250 C until the bulk of the water was 55 removed and a vacuum of 5-20 Torr then applied to the system to remove the final traces of water The vacuum was broken with nitrogen, the product discharged from the reaction vessel and cooled The resulting polyamide had a softening point of 190 C (ASTM D 28-67), 0 7 amine value (ASTM D 2074-66), viscosity of 76 poise at 220 C (ASTM D 445-65) and tensile strength (psi) and elongation (%) of 1800 and 60 400, respectively, determined using ASTM test method D 882-67.
EXAMPLE II
The polyamide resin of Example I was blended with poly(butylene terephthalate) The blended compositions were formulated to contain 2 and 10 weight percent of the additive In addition to the polyamide additive the resin contained six grams zinc stearate per 100 pounds resin as an external lubricant The compositions were then extruded using a three inch, 24 to 1, extruder with an eighthole die and a temperature profile of 420 F (Zone 1), 440 F (Zone 2), 440 F (Zone 5 3), 440 F (Zone 4) and 440 F (die) A control resin containing only the zinc stearate additive was also extruded using the same temperature profile Results of the extrusion were as follows:
Screw Speed Power Output 10 Resin (rpm) (amps) (lbs/hr) Control 39 25 140 Containing 2 Y/ Polyamide Additive 41 23 150 Containing 10 % Polyamide 15 Additive 41 20 150 From the above data it is readily apparent that the addition of the polyamide additive greatly improves the extrusion efficiency It is also apparent that greater output can be achieved without increasing the power requirements of the extruder or, conversely, the same output can be achieved with reduced power consumption 20 Employing only 2 % of the polyamide additive with the poly(butylene terephthalate) resulted in a 7 % increase in output with an 8 % reduction in power consumption In addition to these advantages the products containing the polyamide additive were easily pelletized and there was no substantial decrease in the rate of crystallization.
Since extruder temperatures can be reduced by use of these processing aids 25 product degradation during processing is minimized.
In addition to being an effective processing aid at low levels the additive does not significantly modify the mechanical and thermal properties of the poly(butylene terephthalate) To demonstrate this point a comparison of the modified resin containing 2 % polyamide and unmodified resin was made and the results were 30 as follows:
unmodified Modified Resin Resin Impact (ftlbs/inch notch) ASTM D 256 0 52 0 50 Tensile Strength At Yield (psi)-ASTM D 638 8,700 8,500 35 Elongation At Fail (%) ASTM D 638 23 11 Elastic Modulus (psi) ASTM D 638 340,000 340,000 Flexural Strength At Yield (psi)-ASTM D 790 B 12,700 12,400 Flexural Modulus (psi) ASTM D 970 B 360,000 360,000 The melt point of the modified and unmodified resins, as determined by 40 differential scanning calorimetry, was not appreciably different.
The polyamide additive was also incorporated into the poly(butylene terephthalate) at a 20 weight percent level In addition to improving the processing characteristics of the resin, the rate of crystallization of the extruded poly(butylene terephthalate) was not substantially decreased The use of high levels of 45 the polyamide also permits the processing of some previously unextrudable blends.
EXAMPLE III
The polyamide resin of Example I was blended with a clear, amorphous, grade poly(ethylene terephthalate) resin in a high-speed Henschel mixer for two minutes and the blend containing two weight percent of the polyamide extruded The 50 extrusion was conducted as described in Example II except that the temperature profile was 500 F, 550 F, 5500 F, 550 F and 550 F The processability of the blend was greatly improved over the control resin which contained none of the polyamide additive Similar improved processability was observed using a dry crystallized grade of poly(ethylene terephthalate) 55 EXAMPLE IV
To further demonstrate the effectiveness of the polyamide additives a mineral filled resin composition was prepared as follows:
Poly(ethylene terephthalate) 69 parts Talc 30 parts 60 Polyamide Additive 1 part 1,586,505 A 7 1 850 7 The ingredients were blended in a Henschel high-speed mixer and the blend extruded using a 4-1/2 inch, 24 to 1 vented extruder with a temperature profile of 500 F, 520 F, 520 F, 520 F and 540 F Good mixing was obtained at an output of 350 lbs/hr with a screw speed of 40 rpm using the blend containing the polyamide additive A filled composition not containing the polyamide additive was difficult 5 to extrude and marked variations in the output were obtained because of poor mixing.
EXAMPLE V
Using a procedure similar to that described in Example I, 0 261 equivalent C 36 dimer acid, 0 112 equivalent azelaic acid, 0 073 equivalent hexamethylenediamine 10 and 0 292 equivalent ethylenediamine were reacted to produce a high molecular weight polyamide resin having a softening point of 175 C, tensile strength of 2000 psi and elongation of 320 o/ When this polyamide is incorporated in poly(ethylene terephthalate), poly(butylene terephthalate) or poly( 1,4 cyclohexylenedimethylene terephthalate) at levels ranging from about 1 % up to about 10 % marked 15 improvement in the processing characteristics and rheological properties of the blends is observed.
EXAMPLE VI
The poly(butylene terephthalate) composition of Example II containing 10 % 1 polyamide was extruded into monofilaments The filaments were obtained without 20 difficulty and both the oriented and unoriented filaments exhibited useful characteristics Also, a blend of poly(butylene terephthalate) and 20 weight percent polyamide was extruded using a 2-1/2 inch extruder with a 4-hole die and a temperature profile of 420 F, 440 F, 440 F, 440 F and 460 F The gauge of the original filament obtained from the extruder was 0 100 «, however, the filaments 25 were heat stretched ( 4:1 ratio) so that the final filament gauge was 0 050 » The processability of these blends was excellent and no difficulties were encountered during the extruding and drawing operations Also, the draw tension required to heat stretch the 0 050 » filament was about half that required to produce a similar gauge filament using poly(butylene terephthalate) not containing the polyamide 30 additive.
EXAMPLE VII
A polyamide resin was obtained by reacting 0 289 equivalent C 36 dimer acid, 0.050 equivalent azelaic acid, 0 063 equivalent hexamethylenediamine and 0 250 equivalent ethylenediamine in accordance with the procedure described in 35 Example I The resulting polyamide resin had a softening point of 137 C and tensile strength of 810 psi at 170 % elongation This resin is an effective additive for poly(ethylene terephthalate) and brominated copolyesters to improve the processing characteristics of the resins.
EXAMPLE VIII 40 Blends of both poly(ethylene terephthalate) and poly(butylene terephthalate) containing 2 % of the polyamide of Example I were injection molded in accordance with the standard recommended practice for injection molding specimens of thermoplastic materials (ASTM D 1130-63) employing a mold design as shown in Figure 4 of ASTM D 647 The compositions containing the polyamide additive 45exhibited superior processability as compared to resins which did not contain the additive and the character of the moldings was also significantly improved.
EXAMPLE IX
The polyamide of Example I was blended with a clear amphorous copolyester derived from terephthalic acid, isophthalic acid and cyclohexamethylene 50 dimethanol (Kodar A 150) The blend containing 2 weight percent of the polyamide was extruded as described in Example II except that the temperature profile was 480 F, 480 F, 480 F, 500 F and 480 F The processability of the blend was greatly improved over the control resin which contained none of the additive and the power required was decreased by 5 % 55

Claims (1)

WHAT WE CLAIM IS:-
1 A process for improving the properties of thermoplastic polyester and copolyester resins which comprises incorporating therein 0 01 % to 20 % by weight based on said resin of a high molecular weight polyamide additive containing radicals of a high molecular weight aliphatic or cycloaliphatic dibasic acid 60 containing from 18 to 52 carbon atoms and from 0 to 30 weight percent, based on the acid radicals, of a short-chain, saturated, aliphatic dibasic acid containing from 1.586505 8 1,586,505 8 2 to 13 carbon atoms and 90-110 equivalent percent radicals of an aliphatic saturated diamine containing from 2 to 10 carbon atoms or a mixture of said diamines.
2 A process according to Claim 1 where the polyamide additive has a number S average molecular weight from 10,000 to 35,000, a softening point in the range 5 C to 240 C and amine value less than 20, preferably less than 3.
3 A process according to Claim 1 or 2, wherein the thermoplastic resin is selected from the group consisting of poly(ethylene terephthalate), poly(butylene terephthalate), poly( 1,4 cyclohexylenedimethylene terephthalate) and copolyesters thereof 10 4 A process according to any of Claims 1-3 wherein the polyamide radicals are derived from a high molecular weight dibasic acid containing 75 % or more C 36 dimer acid obtained by the dimerization of C,8 unsaturated monocarboxylic acids.
A process according to any of Claim 1-4 wherein the high molecular weight dibasic acid radicals are saturated and contain 90 O/ or more C 36 of dimer 15 acid radicals.
6 A process according to any of Claim 1-5 wherein the short-chain, saturated, aliphatic dibasic acid radicals contain from 6 to 13 carbon atoms and constitute from 1 to 20 weight percent of the total dibasic acid charge and the diamine radicals are a mixture of two diamines, said diamines differing by at least 3 20 carbon atoms with the longer chain diamine constituting from about 50, to 35 %,, based on equivalents, of the total diamine charge.
7 A process according to any of the Claims 1-6 wherein the thermoplastic resin is selected from the group consisting of poly(ethylene terephthalate), poly(butylene terephthalate), poly(l,4 cyclohexylenedimethylene terephthalate) and 25 copolyesters thereof and the polyamide has a number average molecular weight in the range 10,000 to 35,000, softening point in the range 150 C to 210 C and amine value less than one and is present in an amount from 0 1 I to 10 % by weight.
8 An improved resin composition comprising a thermoplastic polyester or copolyester resin and from 0 01 to 20 % by weight, based on the weight of said resin, 30 of a high molecular weight polyamide containing radicals of a high molecular weight aliphatic or cycloaliphatic dibasic acid having from 18 to 52 carbon atoms and up to 30 weight percent, based on the total dibasic acid charge, of a shortchain, saturated, aliphatic dibasic acid containing from 2 to 13 carbon atoms and radicals of an aliphatic, saturated diamine containing from 2 to 10 carbon atoms or 35 a mixture of said diamines, said polyamide having a number average molecular weight from 5,000 to 50,000, a softening point in the range 100 C to 240 C and amine value less than twenty, preferably less than three.
9 The composition of Claim 8 wherein the thermoplastic resin is selected from the group consisting of poly(ethylene terephthalate), poly(butylene terephthalate), 40 poly(l,4 cyclohexylenedimethylene terephthalate) and copolyesters thereof and the polyamide is derived from a high molecular weight dibasic acid containing 750, or more C 36 dimer acid, obtained by the dimerization of C 18 unsaturated monocarboxylic acids, and having an acid value in the range 180 to 215, saponification value in the range 190 to 205 and neutral equivalent from 265 to 310, 45 from 1 to 20 weight percent, based on the total dibasic acid charge, of a saturated, aliphatic dibasic acid containing from 6 to 13 carbon atoms and a mixture of two diamines, said diamines differing by at least three carbon atoms with the long-chain diamine constituting from about 5 % to 35 %, based on equivalents, of the total diamine charge 50 The composition of Claim 9 wherein the polyamide has a number average molecular weight in the range 10,000 to 35,000, a softening point in the range 150 C to 210 C and amine value less than one.
11 The composition of Claim 10 wherein the radicals of the high molecular weight dibasic acid are saturated and contain 90 % or more C 36 dimer acid and the 55 diamine radicals stem from a mixture of ethylenediamine and hexamethylenediamine.
12 A composition as claimed in Claim 8 substantially as described herein with reference to any one of the Examples II-IX.
J E FARNDON, Chartered Patent Agent.
Printed for Her Majesty’s Stationery Office, by the Courier Press, Leamington Spa, 1981 Published by The Patent Office, 25 Southampton Buildings, London, WC 2 A l AY, from which copies may be obtained.

GB36960/77A
1976-09-07
1977-09-05
Polyester compositions

Expired

GB1586505A
(en)

Applications Claiming Priority (1)

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Title

US05/720,555

US4066587A
(en)

1976-09-07
1976-09-07
Thermoplastic polyester compositions containing polyamide additives

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GB1586505A
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GB1586505A
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1981-03-18

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1976-09-07
1977-09-05
Polyester compositions

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US4066587A
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JPS5331758A
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(1)

BE858474A
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(1)

CA1069641A
(en)

DE
(1)

DE2740115A1
(en)

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DK396277A
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ES462199A1
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FR2363604A1
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GB
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GB1586505A
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IE45581B1
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IT1143679B
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Stabilized polyalkylene terephthalate resin composition

1976

1976-09-07
US
US05/720,555
patent/US4066587A/en
not_active
Expired – Lifetime

1977

1977-09-05
GB
GB36960/77A
patent/GB1586505A/en
not_active
Expired

1977-09-05
IE
IE1836/77A
patent/IE45581B1/en
unknown

1977-09-05
JP
JP10597777A
patent/JPS5331758A/en
active
Pending

1977-09-06
FR
FR7727008A
patent/FR2363604A1/en
not_active
Withdrawn

1977-09-06
DK
DK396277A
patent/DK396277A/en
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1977-09-06
DE
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patent/DE2740115A1/en
not_active
Withdrawn

1977-09-06
CA
CA286,141A
patent/CA1069641A/en
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Expired

1977-09-07
IT
IT27360/77A
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active

1977-09-07
LU
LU78098A
patent/LU78098A1/en
unknown

1977-09-07
NL
NL7709856A
patent/NL7709856A/en
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Application Discontinuation

1977-09-07
BE
BE180727A
patent/BE858474A/en
unknown

1977-09-07
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ES462199A
patent/ES462199A1/en
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DK396277A
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1978-03-08

BE858474A
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1978-03-07

US4066587A
(en)

1978-01-03

JPS5331758A
(en)

1978-03-25

NL7709856A
(en)

1978-03-09

LU78098A1
(en)

1979-05-23

IE45581B1
(en)

1982-10-06

DE2740115A1
(en)

1978-03-16

ES462199A1
(en)

1978-12-16

IE45581L
(en)

1978-03-07

FR2363604A1
(en)

1978-03-31

CA1069641A
(en)

1980-01-08

IT1143679B
(en)

1986-10-22

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