CA1240436A - Reinforced polyester composition having an improved strength - Google Patents
Reinforced polyester composition having an improved strengthInfo
- Publication number
- CA1240436A CA1240436A CA000427497A CA427497A CA1240436A CA 1240436 A CA1240436 A CA 1240436A CA 000427497 A CA000427497 A CA 000427497A CA 427497 A CA427497 A CA 427497A CA 1240436 A CA1240436 A CA 1240436A
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/40—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- 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
-
- 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
Abstract
A REINFORCED POLYESTER COMPOSITION
HAVING AN IMPROVED STRENGTH
ABSTRACT OF THE DISCLOSURE
The present invention is directed to a thermoplastic molding composition comprising a high molecular weight polyethylene terephthalate having an intrinsic viscosity of at least of 0.4 deciliters per gram, a reinforcing amount of a reinforcing agent, a crystallization rate promoter, and a polyepoxy compound which contains more than two terminal epoxy functionalities per molecule. The composition of the invention is characterized by its improved mechanical properties especially its tensile strength and unnotched Izod impact strength. In a preferred embodiment the process for the preparation of the composition of the invention entails treating the reinforcing agent with the polyepoxy compound prior to compounding.
HAVING AN IMPROVED STRENGTH
ABSTRACT OF THE DISCLOSURE
The present invention is directed to a thermoplastic molding composition comprising a high molecular weight polyethylene terephthalate having an intrinsic viscosity of at least of 0.4 deciliters per gram, a reinforcing amount of a reinforcing agent, a crystallization rate promoter, and a polyepoxy compound which contains more than two terminal epoxy functionalities per molecule. The composition of the invention is characterized by its improved mechanical properties especially its tensile strength and unnotched Izod impact strength. In a preferred embodiment the process for the preparation of the composition of the invention entails treating the reinforcing agent with the polyepoxy compound prior to compounding.
Description
Mo-?391 P~-143 A REINFORCED P~LYF.STER COMPOSITION
HAVI~G AN IMPROVED STREN~.TH
FIE~.D OF THE INVENTION
The inv~ntion is directed to thermopl~stic polyester compositions and, more particularlv, to compositions comprising reinforced poly(alkylene tere-phthalate).
BRIEF DESCRIPTION OF THE INVENTION
Reinforced poly(ethylene terephthalate) is imparted improved mechanical properties by the addition of an effective amount of polyepoxy compound having more than two epoxy functionalities per molecule and a small amount of a crystallization rate promoter thereto.
A process or the preparation of a glass fiber reinforced polyethylene terephthalate compositon which entails applying said epoxy to the glass fibers is also disclosed.
BACKGROUND OF THE_INVENTION
Polv(ethylene terephthalates) are use~ul thermoplastic resins that because of their excellent physical properties, such as wear resistance, durabilitY
and dimensional stability, find wide usage in the manufacture of fibers, films and molded articles. The level of their mechanical properties has been disclosed to be improved upon ~he incorporation of reinforcing a~ents therewith, for instance, glass fibers (British Patent 1,111,012, U. S. Patents 3,368,995, 4,123,415 and DAS 2,042,447).
The art is noted to include U. S. Patent 39632,402 which discloses molding compositions based on sa~urated polyesters containi~g9 inter alia, a certain polyunctional epoxy, which compositions are character-Mo-2391 ~`
~.
~ f~ ~
- la -ized in tha~ their mechanical properties are maintained.
Also, U. S. Patent 4,229,553 is noted to disclose poly-(alkylene terephthalatP) moldin~ materials containing a diepoxide as a thermal stabilizer.
Mo-2391 Further, U. S. Patent 3,886,104 is noted to disclose glass reinforced poly(alkylene terephth~-late) cnmpositions rendered thermally stable by the addition of certain internal polyfunctional epoxides, and British Patent 2,015,014 is noted to disclose an epoxy formed from bisphenol A and epichlorohydrin as an additive to certain glass fiber reinforced poly(ethylene terephthalate) compositions. Rritish Patent 1,224,684 discloses compositions consisting of polyethylene terephthalate, a nucleating agent and a compound having two terminal epoxy groups, said to offer advantages in terms of rate of crystallization and the absence of flash formation. Also, U. S. Patent 3,843,615 is noted to teach certain epoxides as cross-linking agents in polyesters. The process for producing foamed articles of aromatic polyesters taught in U. S. Patent 4,284,596 is noted to entail a composition comprising polyepoxy compounds having at least two epoxy groups in the molecule. Among the polyepoxy compounds (at column 7, lines 1-5) there is described an epoxy compound suitable in the present invention.
European Patent Application 10 t 773 is directed to thermoplastic polyester compounds having improved impact str~n~th and containing an epoxy compound and an organic sulfonate and/or an organic sulfate salt.
DETAILED DESCRIPTIOM OF THE INVENTION
The high molecular weight, thermoplastic polyester resins suitable in the practice of the invention are derived from an aromatic dicarboxylic acid and a diol component and are characterized in that their intrinsic viscosity is at least 0.4 deciliters per gram.
Op~ionally, the aromatic dicarboxylic acid component accounts for a~ least B5 mole percent of the Mo-2391 - 2a -dicarboxylic acid co~ponent. Among the suitable aromatic dicarboxylic acid~ are terephthalic acid, isophthalic acid, naphthalene-dicarboxylic acid, diphenylP,therdicarbox-Mo-2391 ylic acid, diphenyldicarboxylic acid, diphenylsulfone dicarboxylic acid and diphenoxyethane dicarboxylic acid. The optional, at most 15 mole percent of the acid componenk which is not aromatic dicarboxylic, may be repr~sented by hydroxycarboxylic acids and by aliphatic dicarboxylic acids such as succinic acid, adipic acid and sebacic acid.
The diol component of these polyesters may contain from 2 to 10 carbon atoms, preferably from 2 to 4 carbon atoms in the form of linear methylene chains with up to 30 mole percent of one or more other aliphatic diols having 3 to 8 carbon atoms, cycloaliphatic diols having ~rom 6 to 15 carbon atoms or aromatic diols having from 6 to 21 carbon atoms.
Examples of such additional diols ~"codiols") include 3-methylpentanediol~(2,4~, 2-methylpentanediol-(1,4),
HAVI~G AN IMPROVED STREN~.TH
FIE~.D OF THE INVENTION
The inv~ntion is directed to thermopl~stic polyester compositions and, more particularlv, to compositions comprising reinforced poly(alkylene tere-phthalate).
BRIEF DESCRIPTION OF THE INVENTION
Reinforced poly(ethylene terephthalate) is imparted improved mechanical properties by the addition of an effective amount of polyepoxy compound having more than two epoxy functionalities per molecule and a small amount of a crystallization rate promoter thereto.
A process or the preparation of a glass fiber reinforced polyethylene terephthalate compositon which entails applying said epoxy to the glass fibers is also disclosed.
BACKGROUND OF THE_INVENTION
Polv(ethylene terephthalates) are use~ul thermoplastic resins that because of their excellent physical properties, such as wear resistance, durabilitY
and dimensional stability, find wide usage in the manufacture of fibers, films and molded articles. The level of their mechanical properties has been disclosed to be improved upon ~he incorporation of reinforcing a~ents therewith, for instance, glass fibers (British Patent 1,111,012, U. S. Patents 3,368,995, 4,123,415 and DAS 2,042,447).
The art is noted to include U. S. Patent 39632,402 which discloses molding compositions based on sa~urated polyesters containi~g9 inter alia, a certain polyunctional epoxy, which compositions are character-Mo-2391 ~`
~.
~ f~ ~
- la -ized in tha~ their mechanical properties are maintained.
Also, U. S. Patent 4,229,553 is noted to disclose poly-(alkylene terephthalatP) moldin~ materials containing a diepoxide as a thermal stabilizer.
Mo-2391 Further, U. S. Patent 3,886,104 is noted to disclose glass reinforced poly(alkylene terephth~-late) cnmpositions rendered thermally stable by the addition of certain internal polyfunctional epoxides, and British Patent 2,015,014 is noted to disclose an epoxy formed from bisphenol A and epichlorohydrin as an additive to certain glass fiber reinforced poly(ethylene terephthalate) compositions. Rritish Patent 1,224,684 discloses compositions consisting of polyethylene terephthalate, a nucleating agent and a compound having two terminal epoxy groups, said to offer advantages in terms of rate of crystallization and the absence of flash formation. Also, U. S. Patent 3,843,615 is noted to teach certain epoxides as cross-linking agents in polyesters. The process for producing foamed articles of aromatic polyesters taught in U. S. Patent 4,284,596 is noted to entail a composition comprising polyepoxy compounds having at least two epoxy groups in the molecule. Among the polyepoxy compounds (at column 7, lines 1-5) there is described an epoxy compound suitable in the present invention.
European Patent Application 10 t 773 is directed to thermoplastic polyester compounds having improved impact str~n~th and containing an epoxy compound and an organic sulfonate and/or an organic sulfate salt.
DETAILED DESCRIPTIOM OF THE INVENTION
The high molecular weight, thermoplastic polyester resins suitable in the practice of the invention are derived from an aromatic dicarboxylic acid and a diol component and are characterized in that their intrinsic viscosity is at least 0.4 deciliters per gram.
Op~ionally, the aromatic dicarboxylic acid component accounts for a~ least B5 mole percent of the Mo-2391 - 2a -dicarboxylic acid co~ponent. Among the suitable aromatic dicarboxylic acid~ are terephthalic acid, isophthalic acid, naphthalene-dicarboxylic acid, diphenylP,therdicarbox-Mo-2391 ylic acid, diphenyldicarboxylic acid, diphenylsulfone dicarboxylic acid and diphenoxyethane dicarboxylic acid. The optional, at most 15 mole percent of the acid componenk which is not aromatic dicarboxylic, may be repr~sented by hydroxycarboxylic acids and by aliphatic dicarboxylic acids such as succinic acid, adipic acid and sebacic acid.
The diol component of these polyesters may contain from 2 to 10 carbon atoms, preferably from 2 to 4 carbon atoms in the form of linear methylene chains with up to 30 mole percent of one or more other aliphatic diols having 3 to 8 carbon atoms, cycloaliphatic diols having ~rom 6 to 15 carbon atoms or aromatic diols having from 6 to 21 carbon atoms.
Examples of such additional diols ~"codiols") include 3-methylpentanediol~(2,4~, 2-methylpentanediol-(1,4),
2,2,4-trimethylpentanediol-(1,3), 2-ethylhexanediol-(1,3), 2,2-diethylpropanediol~(1 t 3), hexanediol-(1,3), 1,4-di-(~-hydroxyethoxy)-benzene, 2,2-his-(4-hydroxycyclohexyl)-propane, 2,4-dihydroxy-1,1,3,3-tetramethyl-cyclobutane, 2,2-bis-(3-~-hydroxy ethoxyphenyl)propane and 2,2-bis-(4-hydroxy-propox~phenyl)-propane.
Typical examples of the diol include polymethylene~ diols such as ethylene glycol, trimethylene glycol, tetramethylene glycol and hexamethylene glycol, neopentyl glycol, cyclohexane dimethylol, tricyclodecane dimethylol, 2j2-bis(4-~-hydroxyethoxyphenyl)propane, 4,4'-bis(~-hydroxyethoxy)diphenylsulfone, and diethylene glycol.
The polyesters may be branched by incorporating trihydric or tetrahydric alcohols or tribasic or tetrabasic acids, as described in German Mo-2391 q~
~ 4 -Offenlegungsschrift 1,900,270 and in U. S. Patent
Typical examples of the diol include polymethylene~ diols such as ethylene glycol, trimethylene glycol, tetramethylene glycol and hexamethylene glycol, neopentyl glycol, cyclohexane dimethylol, tricyclodecane dimethylol, 2j2-bis(4-~-hydroxyethoxyphenyl)propane, 4,4'-bis(~-hydroxyethoxy)diphenylsulfone, and diethylene glycol.
The polyesters may be branched by incorporating trihydric or tetrahydric alcohols or tribasic or tetrabasic acids, as described in German Mo-2391 q~
~ 4 -Offenlegungsschrift 1,900,270 and in U. S. Patent
3,692,744. EY.amples of su~table branching agents include trimesic acid, pyromellitic acid, trimethy]olpropane and eth~ne, and pentaeryth-itol. It is advisable not to use more than 1 ~ole % of branching agent, based on the quantity of acid co~ponent. The polyesters may also contain known monofunctional compounds such as phenol or benzoic aci.d as chain terminators.
The preferred polyesters are characterized in that their structure comprises units of the general formula (I): o C~--~
O~-tCH2)n ~ (I) where n denotes 2 to 4.
The most preferred poly(alkylene terephthalate) in the present context is poly(ethylene terephthalate).
The intrinsic viscosity characterizing the suitable polyester resins in the practice according to the invention should preferably be in the range of 0.4 to 1.4 grams per deciliter and, more preferably, between 0.4 and 0.8 grams per deciliter, as measured in a 1%
solution of phenol and tetrachloroethane (60:40) at 25C.
Methods for the preparation of the polyester resin suitab3.e in the present con~ext are known and have been described in U. S. Patents 2,465,319 and 3,047,539.
The composition of the invention includes crystallization rate promoters for the polyester such as to allow lower mold ~emperatures and shorter injection cycles.
Mo-2391 ,, 3~:3 - 4a -It is generally believed that- such crystalli~ation rate promoters function by plasticizing the po'yethylene terephthalate matrix and thus al]owing the molecular chains greater mobility to align themselves in a crvstalline array. An unclesired but unavoidable consequence of such plasticization is some loss in the stiffness of the matrix even after the compounded resin has cooled to room temperature after processing. This loss may be manifested in lower mechanical properties. The present invention is concerned with compensating for such a loss without impairing the crystallization rat~ promotin~ effect by the addition of certain polvepoxides.
Mo-2391 i i ;
~2~
A~on~ the most suitahle co~pounds to be emploved ~s crvstallization rat~ promoters are oligomeric polvesters whlch consist of structural units of the formula (1~ or (2) (1) ~2) ~ O-C ~ R ~ oRl~ /C p<l o~_ or mixtures thereof whereln Rl denotes a linear or branched aliphatic t cycloaliphatic or araliphatic divalent radical with 2 to 20 C atoms, preferably 2 to 10 C atoms, R2 denotes a linear or branched aliphatic, cycloaliphatic, araliphatic or aromatic divalent radical of 2 to 20, preferably 3 to 10 C atoms, and x denotes an integer of at least 2, up to any value giving the oligomer a number-average molecular weight of 6000 or less, preferably about 600 to 3000, y is an integer o 0 or 1, in the former case the oligomer is an aliphatic polycarbonate which is a special type of polyester.
Of course, mixtures of different compounds which fall under the above formula can also be employed.
Preferred oligomeric polyesters are those which are derived from the ollowing acids and alcohols: di- -and tricar~oxylic acids, adipic acid, Mo-2391 . .
azelaic acid, citric acid C(OH3(COOH)(CH2COOH)2 fumaric, maleic acid HOOCHC=CHCOOH ~lutarlc acid, phthalic, isophthalic, terephthalic acid, trimellitic acid, trimesitinic acid, succinic acid, tartaric acid HooC(CHOH~2COOH sebacic acid, monocarboxylic aci.ds, cresotic acid, salicyclic acid, acetic ac-id, isobutyric acid, caproic acid, caprylic acid, pelar~onic acid, 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid CH3(CH2)7CH=CH(CH2)7COOH t ricinolic acid CH3~CH2)5CHiOH)CH2CH=CH~C~1)7COOH~
2-ethylbutyric acid, behenic acid, benzoic acid, abictic acid, 2-phenylbutyric acid, tall oil, fatty acid, di- and higher functional alcohols, ethylene glycol, propane diol 1,3/1,2, butanediol 1,3/1,4, pentanediol 1,.5, hexanediol 1,6, dipropylene glycol 1,3/1,2, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol M 400, neopentyl glycol HO-CH2-C(CH3)2-CH20H, glycerol HOCH2 CHOH-CH20H, trimethylolethane CH3C(CH~OH)3l trimethylolpropane C2H5C(CH20H33, pentaerythritol C~CH20H)4, 2,2,4-trimethyl-1,3-pentanediol, sucrose, monofunctional alcohols, 2-ethylhexanol, isonol, tertiary butanol, methanol, isopropanol C8H17~ CH20 octylbenzyl alcohol, butyl alcohol, isobutyl alcohol, 2-ethylhexanol, isononyl alcohol, n-octyl alcoholl iso-octyl alcohol, n-decyl alcohol, isodecyl alcohol, butoxyethyl alcohol CH3(CH2)3-O(CH2)20H t butoxyethyloxyethyl alcohol Mo-2391 ~r~ f~
~ 7 C~3(CH2)3- 0~c~l2~2o(cH2)2o cyclohexylalcohol, ~1 n hexyl alcohol, tetrahydrourfuryl alcohol, 2-butoxyethyl alcohol CH3 CH~(OCH2CH2OH)-CH2CH3, ethyl alcohol, amyl alcohol, n-undecyl alcohol, tridecyl alcohol, butylbenzyl alcohol, methylcyclohexyl alcohol, methoxyethyl alcohol, benzyl alcohol, allyl alcohol CH2=CH-CH2OH, hydroabietyl alcohol.
Especially preferred oligomers are those using adipic acid or sebacic acid as the dicarboxylic acid, 2-ethylhexane-1,3-diol, 2,2,4-trimethylpentane -1,3-diol, butane-1,3-diol, hexane-1,6-diol or butane-1,4-diol as the diol component and 2-ethylhexanol, 3,5,5-trimethylhexanol or n-butanol as the monohydric alcohol component.
Particularly suitable oligomers are poly-(butane-1,3-diol adipate), poly-(hexane-1,6-diol adipate) and poly-tbutane-1,4-diol adipate).
The polyepoxy compounds suitable in the context of the invention are characterized in having more than two, preferably 3 to 5, most preferably 4, terminal epoxide functionalities per molecule. ~mong the suitable compounds are those described by the general formula~ (II) Mo-2391 ~2~
C C (II) / \O
Rl H
wherein Rl denotes a hydrogen a~om or an alkyl radical, preferably H or a Cl-C4 alkyl radical, and R~ denotes a monovalent radical containing more than one additional terminal epoxide ftmctionality.
Preerably, R2 may be selected from among the group consisting of alkyl, cycloalkyl, polyalkyl, aralkyl, polyaralkyl and aryl radicals, all of which may contain es~er, thioester, amine, amide, ether, ~hioether or ketone groupings with the proviso tha~ in any case R2 con~ains more than one terminal epoxide functionality.
Further suitable polyepoxy compounds suitable in the present practice are the reaction products of chloroalkyl oxiranes with active hydrogen compounds which products may be represented by the general formula, (III) H H
O (III) where R is a Cl-C4 alkylene and R3 is a polyvalent radical having a valence of n.
Mo-2391 ~7 ~~ ~
""lS
- ~ -~ uitabl~ polvepoxides are the polvepo~idized r~actlon products of epichlorohydrin and polvhvdric alcohols such as pe~.taery~hritol; the polvepoxidized reaction products of epi.chlorohydrin and ~etraphenolated hydrocarbons made by the acid catalyzed reaction of phenol and dialdehydes; and the polyepoxidized reaction products of polyamines made by the acid ca~alyzed reaction of anili.ne and formaldehyde.
More specifically preferred polyepoxides in the present context are N,N'-(methylenedi-4,1-phenylene) bis [N-(oxiranylmethyl)-oxirane-methanamine]
(Ciba-Geigy*MY-720), 1,2-ethane diylidenetetrakis (4,1-phenyleneoxy methylene)-tetrakis-oxirane, (Shell Epon~ 1031).
The preparation of the polyepoxy compounds suitable in the practice in accordance with the invention is known in the art and has been described in, among others, British Patent 774,663 and U. S. Patent 3,954,650.
The compositions in accordance with the invention contain a reinforcing amount of a reinforcing agent. Generally, any reinforcing agent can be used, for example fibers, whiskers, platelets of metals or of -:
non-metals (including organic materials such as 25 polyaramid fibers) including aluminum, iron, nickelJ
ceramics 9 carbon filaments, .
~Trademark b:
i, ' Mo-2391 I~
silicates, asbestos, silica, mlca and glass. In the present context, a reinforcing agent is one, or more, of the above that adds to any of the strength, stiffness or impact properties of the matrix wherein it has been incorporated.
Although it is only necessary to have at least a reinforcing amount of the reinforcing agent incorporated in their matrix, the present compositions comprise from about 5 to about 60, preferably about 10 ~o about 50 9 percent by weight of reinforcing agents, the percentages being in relation to the total weight of the polyester and reinforcing agents.
The preferred reinforcing agent is glass fibers.
Suitable glass fibers in the present context are available in commerce (for instance, PPG* 3540 and OCF* 416CB) and are characterized in that their chemical makeup render them substantially unreactive with the matrix. The known C-glass, S-glass and E glass types are suitable.
Although the length of the glass fibers introduced is not particularly critical to the invention, chopped strands of 1/8 - 1" in length are conveniently used. The length of the fibers in the molded product is generally less than 1/8". The diameter of the glass fibers may average between 5 to 15 microns and it too is not critical to the invention~
although best results are ob~ained using fibers that are 7 to 13 microns in average diameter.
*Trademark Mo-2391 ~ ,~
~ 2 ~ 3 Any effective amo~nt of the polvepoxy compound may be used in the compositlon of this invention. In general, however, the amount of the polyepox~T compound useful in the compositions of the invention is between about 0.05 and 5.0 percent, preferablv 0.08 - 1,0, most preferably between about 0.1 and 0.8, percent relative to the total weight of the polyester resin plus reinforcement.
In general, the best p~operties will be obtained in c~mpositions comprising sized reinforcing agents although as is demonstrated below compositions incorporating unsized reinforcing agents appear to be improved upon the addition of the instant polyepogy which appears to function as a coupling agent.
The method of blending the composition of this invention is not critical and may be carried out by any of the known conventional techniques. In accordance with one procedure, the polyester in powder or granular form, the reinforcing agent and the polyepoxy compound and other suitable additives may be blended and the blend extruded and comminuted into pellets or other convenient form. The composition thus prepared is suitable as a molding composition in a variety of thenmoplastic processes. The following examples illustrate the preparation of compositions within the scope of the present invention. These examples are not to be construed to in any way limit the invention but rather to demonstrate its operability.
The advantages associated with the composition of the invention are attained without resorting to any other additives such as the sulfonate salts or sulfate salts that are disclosed in European Patent Application 10,773.
Mo-2391 i .
~L2 - lla -EXAMPT.ES
Compositions according to the invention nomlnally comprising 70 parts by weight (pbw) of poly(ethylene terephthalate) having an intrinsic Mo-2391 ~ `3 viscosity of about 0.6 dl/gm, a commercial product of Eastman Kodak available under the tracle name of TENITE*
7741~ and 30 pbw of glass fibers (PPG 3540) were prepared and ~ested as shown below. The dependence of the properties on the amount of the polyepoxy added to the compositions is apparent upon a comparison with the control (E~ample l-l) where~o no epoxide was added. In addition to the major c:omponents noted above, the compositions all contained minor amounts of a crystallization rate promoter, a nucleating agent and thermal and hydrolytic stabilizers in accordance ~ith U. S. Patent 4,223,113.
The polyepoxy resin (EPON* 1031) was mîxed into the molten composition by extrusion compounding. The e~truder, a two stage, single screw (2.75:1) equipped with vacuum vent ~etween stages was operated at 65 rpm at a temperature profile of 280/280/270/260/245/275C
(r -~ f).
Component/TextUnit 1~ 2 1-3 1-4 1-5 EPON 1031 conc'n ~ 0 .1 .2 .3 .5 IZOD, l/8 NotchJ/M 79 80 86 97 86 IZOD, 1/8 UnnotchJ/M 660 790550 980 770 25 Tensile @ BreakMPa 129 141147 152 151 Tenslle Retention(l) % 67 86 90 87 93 Flexural ModulusGPa 9.9 9.310.3 9.9 9.9 Flexural StrengthMPa 186 224232 240 _ 225 (l)After ageing, 8 hours at 121C in saturated steam.
*Trademark Mo-2391 , An improvement in the mechanical properties associated with flddltion of polyepoxide is demonstratet]
below t~ be substa~tially independent of the crystallization rate of polv(ethylene terephthalate).
The compositions all nominally based on 70 pbw of PET
(TENITE 7741~ and 30 pbw of glass fibers (PPG 3540~ were prepared by the same procedure described in Example 1 above. The repor~ed values represent averages of several experimental results obtained under generally similar conditions.
Component/Test Unit 2-1 2-2 2-3 2-4 Glass fibers ~ 30 30 30 30 15 Crystallization rate promoter(l) % 0 0 4.9 4.9 Polyepoxy(4) % 0 0.30 0 0.30 Izod N(2) 1/8 J/M 96.8 97 90 98.2 Izod UNN(3) 1/8 J/M 979 989 726 860 Tensile @ Break MPa 148 163 138 151 Aged 16 hr. 410F MPa 96 127 93 125 Flexural Modulus GPa 10.1 10.2 9.8 10 Flexural Strength MPa 230 254 205 234 (1) Polyhexane diol adipate (MW ahout 2000) (2) Notched specimens (3) Unnotched specimens ~4) Epon 103 * Trademark Mo-2391 EXAMPE _3 The compositions which properties are compared below were pr~pared in accordance with the procedure outlined above in Example 1 and are indicated to further demonstrate the efficacy of the polyepoxide additive in the present context. The polyester component used was TENITE 7741.. Polyhexane diol adipate, a crystallization rate promoter at a level of 4.9% was added to each of the compositions.
Component/TestUnit3-1 3-2 3-3 3-4 Conc'n 419AA(1) 41gAA(1) 3540(2) 3540( ) Conc'n % 30 30 30 30 EPON 1031 conc'n % 0 0.3 0 3 IZOD, 1/8 NotchJ/M102 105 79 89 IZOD9 1/8 Unnotch J/M 640 400 660 800 Tensile @ Break MPa135 141 130 152 Elong'n % 2 3 2 2 Flexural Stren~th MPa 197 212 193 235 (l)A product of Owens Corning Fiberglas Corp.
(2)A product of PPG, Inc.
Mo-2391 The series of experiments summarized in Table 4 demonstrates the efficacv of the polyepoxy compounds of the invention in imparting desirable mechanical properties to glass reinforced thermoplastic polyesters and compares these with the corresponding properties of the compositions modified with polyepoxides outside the present scope. Following the same preparation procedure as outlined above, the compositions were prepared, tested and evaluated as below. The compositions all comprised nominally, 70 pbw of PET (TENITE* 7741), 30 pbw of glass fiber (PPG* 3540) and about 4.9% of polyhexane diol adipate (~ about 2000) as a crystallization rate promoter.
Mo-2391 L ~D ~ ~
TA~LE 4 .
C~onent/ 4~1 4-2 4-3 4-4 4-5 4-6 4-7 Test Unit Intern~es ~lone 'l~ EPOXIDES
Epoxide EunctionalityNo. 2 4 5 none 1 2 4 EE~oxide Type(13 _ A B C -- X Y Z
Epoxide conc'n % 0.5 0.5 0.5 0 0.6 0.5 0.3 IZOD, 1/8 No~ch J/M 71 71 71 79 94 87 89 IZOD,1/8 Unnotch J/M460 510 540 660 480 470 800 10 Tensile @ Break MPa 136 138 141 130 95 142 . 152 Tensile Petention(2) % 80 84 88 67 78 92 89 Flex~ral Strenath MPa 198 200 208 190 168 231 235 15 (l)A = Epox~dized butyl ester of linseed oil B - EFoxidized soy bean oil C = Epoxidized linseed oil X = Phenyl glycidyl ether Y = EPA~Epichlor~hydrin reac~ion product 20 Z = Ethanediylidenetetrakis~4,1-phenyleneo~y methoxy)tetrakis-oxirane, homopolymer (2)After agemg 8 hours at 121C in saturated ste~n Mo-2391 Table 4 compares the efficacy of polyepoxides containing internal oxirane groupings such as those oE epoxidi~ed vegetable oils with polyepoxides containing terminal oxiranes such as those found in EPON 1031 with the reaction products of epichloro-hydrin with BPA. The table indicates:
a) ~ comparison of 4-5 with 4-4 shows that a terminal monoepoxide is not only not strength enhancing but is actually deleterious to strength development in the model reinforced, crystallizable P~T formulation.
b) The series 4-1 through 4-3 and 4-5 through 4 7 show that the action of the epoxide function in improving the strenyth and ductility of reinforced P~T is roughly proportional to the number of epoxides in the molecule~ Of particular importance in light of prior art, is the comparison of 4-7 with 4-6 which shows the significantly improved ductility and strength resulting from use of a tetrafunctional epoxide such as EPON 1031 as compared with the model composition modified with the difunctional epichlorohydrin/~P~ type epoxy re~in.
c~ The contrasts of 4-6 with 4-1 and 4-7 with 4-2 indicate that the terminal epoxides, particularly the terminal epoxides of the resins disclosed in this invention are significantly more efficient than internal epoxides such as those shown in the example and disclosed in U.S. Patent 3,886,104.
The epoxide in accordance with the inventionis shown upon comparing the properties of the composition of Example 5 to act as a coupling agent in the system of poly(alkylene terephthalate) glass Mo-2391 '~2~ 6 - 18 ~
reinforcementO The polyester and glass ,were as in Example 1 and the preparation of the compositions was in accorda~ce with the procedure outlined there.
A~;[E
5Component/Test Unit _ 5-1 5-2 5-3 Glass type(l) _861X10(3)861X10( ) 861X10( treatedsized EEON 1031 Conc'n ~ 0 0.15 0.15 IZOD 1/8 Notched J/M 52 74 62 10 IZOD 1/8 Unnotched J/M 370 640 420 Tensile @ ~ailure MPa 99 128 118 Flexural Mcdulus Gæa 8.8 9.6 9.3 Flexural Strength MPa 130 190 178 HD~ 264 psi C 1?2 216 _ 215 (1)861X10 is a glass oDntaining no organic material on its surface (2)861X10 treated with EPCN 1031 in a solvent, then heat-treated to drive off the solvent and ccmplete the SiOH/oxirane reaction.
(3)861X10 treated as in (2) but without the EPCN 1031.
The preferred polyesters are characterized in that their structure comprises units of the general formula (I): o C~--~
O~-tCH2)n ~ (I) where n denotes 2 to 4.
The most preferred poly(alkylene terephthalate) in the present context is poly(ethylene terephthalate).
The intrinsic viscosity characterizing the suitable polyester resins in the practice according to the invention should preferably be in the range of 0.4 to 1.4 grams per deciliter and, more preferably, between 0.4 and 0.8 grams per deciliter, as measured in a 1%
solution of phenol and tetrachloroethane (60:40) at 25C.
Methods for the preparation of the polyester resin suitab3.e in the present con~ext are known and have been described in U. S. Patents 2,465,319 and 3,047,539.
The composition of the invention includes crystallization rate promoters for the polyester such as to allow lower mold ~emperatures and shorter injection cycles.
Mo-2391 ,, 3~:3 - 4a -It is generally believed that- such crystalli~ation rate promoters function by plasticizing the po'yethylene terephthalate matrix and thus al]owing the molecular chains greater mobility to align themselves in a crvstalline array. An unclesired but unavoidable consequence of such plasticization is some loss in the stiffness of the matrix even after the compounded resin has cooled to room temperature after processing. This loss may be manifested in lower mechanical properties. The present invention is concerned with compensating for such a loss without impairing the crystallization rat~ promotin~ effect by the addition of certain polvepoxides.
Mo-2391 i i ;
~2~
A~on~ the most suitahle co~pounds to be emploved ~s crvstallization rat~ promoters are oligomeric polvesters whlch consist of structural units of the formula (1~ or (2) (1) ~2) ~ O-C ~ R ~ oRl~ /C p<l o~_ or mixtures thereof whereln Rl denotes a linear or branched aliphatic t cycloaliphatic or araliphatic divalent radical with 2 to 20 C atoms, preferably 2 to 10 C atoms, R2 denotes a linear or branched aliphatic, cycloaliphatic, araliphatic or aromatic divalent radical of 2 to 20, preferably 3 to 10 C atoms, and x denotes an integer of at least 2, up to any value giving the oligomer a number-average molecular weight of 6000 or less, preferably about 600 to 3000, y is an integer o 0 or 1, in the former case the oligomer is an aliphatic polycarbonate which is a special type of polyester.
Of course, mixtures of different compounds which fall under the above formula can also be employed.
Preferred oligomeric polyesters are those which are derived from the ollowing acids and alcohols: di- -and tricar~oxylic acids, adipic acid, Mo-2391 . .
azelaic acid, citric acid C(OH3(COOH)(CH2COOH)2 fumaric, maleic acid HOOCHC=CHCOOH ~lutarlc acid, phthalic, isophthalic, terephthalic acid, trimellitic acid, trimesitinic acid, succinic acid, tartaric acid HooC(CHOH~2COOH sebacic acid, monocarboxylic aci.ds, cresotic acid, salicyclic acid, acetic ac-id, isobutyric acid, caproic acid, caprylic acid, pelar~onic acid, 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid CH3(CH2)7CH=CH(CH2)7COOH t ricinolic acid CH3~CH2)5CHiOH)CH2CH=CH~C~1)7COOH~
2-ethylbutyric acid, behenic acid, benzoic acid, abictic acid, 2-phenylbutyric acid, tall oil, fatty acid, di- and higher functional alcohols, ethylene glycol, propane diol 1,3/1,2, butanediol 1,3/1,4, pentanediol 1,.5, hexanediol 1,6, dipropylene glycol 1,3/1,2, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol M 400, neopentyl glycol HO-CH2-C(CH3)2-CH20H, glycerol HOCH2 CHOH-CH20H, trimethylolethane CH3C(CH~OH)3l trimethylolpropane C2H5C(CH20H33, pentaerythritol C~CH20H)4, 2,2,4-trimethyl-1,3-pentanediol, sucrose, monofunctional alcohols, 2-ethylhexanol, isonol, tertiary butanol, methanol, isopropanol C8H17~ CH20 octylbenzyl alcohol, butyl alcohol, isobutyl alcohol, 2-ethylhexanol, isononyl alcohol, n-octyl alcoholl iso-octyl alcohol, n-decyl alcohol, isodecyl alcohol, butoxyethyl alcohol CH3(CH2)3-O(CH2)20H t butoxyethyloxyethyl alcohol Mo-2391 ~r~ f~
~ 7 C~3(CH2)3- 0~c~l2~2o(cH2)2o cyclohexylalcohol, ~1 n hexyl alcohol, tetrahydrourfuryl alcohol, 2-butoxyethyl alcohol CH3 CH~(OCH2CH2OH)-CH2CH3, ethyl alcohol, amyl alcohol, n-undecyl alcohol, tridecyl alcohol, butylbenzyl alcohol, methylcyclohexyl alcohol, methoxyethyl alcohol, benzyl alcohol, allyl alcohol CH2=CH-CH2OH, hydroabietyl alcohol.
Especially preferred oligomers are those using adipic acid or sebacic acid as the dicarboxylic acid, 2-ethylhexane-1,3-diol, 2,2,4-trimethylpentane -1,3-diol, butane-1,3-diol, hexane-1,6-diol or butane-1,4-diol as the diol component and 2-ethylhexanol, 3,5,5-trimethylhexanol or n-butanol as the monohydric alcohol component.
Particularly suitable oligomers are poly-(butane-1,3-diol adipate), poly-(hexane-1,6-diol adipate) and poly-tbutane-1,4-diol adipate).
The polyepoxy compounds suitable in the context of the invention are characterized in having more than two, preferably 3 to 5, most preferably 4, terminal epoxide functionalities per molecule. ~mong the suitable compounds are those described by the general formula~ (II) Mo-2391 ~2~
C C (II) / \O
Rl H
wherein Rl denotes a hydrogen a~om or an alkyl radical, preferably H or a Cl-C4 alkyl radical, and R~ denotes a monovalent radical containing more than one additional terminal epoxide ftmctionality.
Preerably, R2 may be selected from among the group consisting of alkyl, cycloalkyl, polyalkyl, aralkyl, polyaralkyl and aryl radicals, all of which may contain es~er, thioester, amine, amide, ether, ~hioether or ketone groupings with the proviso tha~ in any case R2 con~ains more than one terminal epoxide functionality.
Further suitable polyepoxy compounds suitable in the present practice are the reaction products of chloroalkyl oxiranes with active hydrogen compounds which products may be represented by the general formula, (III) H H
O (III) where R is a Cl-C4 alkylene and R3 is a polyvalent radical having a valence of n.
Mo-2391 ~7 ~~ ~
""lS
- ~ -~ uitabl~ polvepoxides are the polvepo~idized r~actlon products of epichlorohydrin and polvhvdric alcohols such as pe~.taery~hritol; the polvepoxidized reaction products of epi.chlorohydrin and ~etraphenolated hydrocarbons made by the acid catalyzed reaction of phenol and dialdehydes; and the polyepoxidized reaction products of polyamines made by the acid ca~alyzed reaction of anili.ne and formaldehyde.
More specifically preferred polyepoxides in the present context are N,N'-(methylenedi-4,1-phenylene) bis [N-(oxiranylmethyl)-oxirane-methanamine]
(Ciba-Geigy*MY-720), 1,2-ethane diylidenetetrakis (4,1-phenyleneoxy methylene)-tetrakis-oxirane, (Shell Epon~ 1031).
The preparation of the polyepoxy compounds suitable in the practice in accordance with the invention is known in the art and has been described in, among others, British Patent 774,663 and U. S. Patent 3,954,650.
The compositions in accordance with the invention contain a reinforcing amount of a reinforcing agent. Generally, any reinforcing agent can be used, for example fibers, whiskers, platelets of metals or of -:
non-metals (including organic materials such as 25 polyaramid fibers) including aluminum, iron, nickelJ
ceramics 9 carbon filaments, .
~Trademark b:
i, ' Mo-2391 I~
silicates, asbestos, silica, mlca and glass. In the present context, a reinforcing agent is one, or more, of the above that adds to any of the strength, stiffness or impact properties of the matrix wherein it has been incorporated.
Although it is only necessary to have at least a reinforcing amount of the reinforcing agent incorporated in their matrix, the present compositions comprise from about 5 to about 60, preferably about 10 ~o about 50 9 percent by weight of reinforcing agents, the percentages being in relation to the total weight of the polyester and reinforcing agents.
The preferred reinforcing agent is glass fibers.
Suitable glass fibers in the present context are available in commerce (for instance, PPG* 3540 and OCF* 416CB) and are characterized in that their chemical makeup render them substantially unreactive with the matrix. The known C-glass, S-glass and E glass types are suitable.
Although the length of the glass fibers introduced is not particularly critical to the invention, chopped strands of 1/8 - 1" in length are conveniently used. The length of the fibers in the molded product is generally less than 1/8". The diameter of the glass fibers may average between 5 to 15 microns and it too is not critical to the invention~
although best results are ob~ained using fibers that are 7 to 13 microns in average diameter.
*Trademark Mo-2391 ~ ,~
~ 2 ~ 3 Any effective amo~nt of the polvepoxy compound may be used in the compositlon of this invention. In general, however, the amount of the polyepox~T compound useful in the compositions of the invention is between about 0.05 and 5.0 percent, preferablv 0.08 - 1,0, most preferably between about 0.1 and 0.8, percent relative to the total weight of the polyester resin plus reinforcement.
In general, the best p~operties will be obtained in c~mpositions comprising sized reinforcing agents although as is demonstrated below compositions incorporating unsized reinforcing agents appear to be improved upon the addition of the instant polyepogy which appears to function as a coupling agent.
The method of blending the composition of this invention is not critical and may be carried out by any of the known conventional techniques. In accordance with one procedure, the polyester in powder or granular form, the reinforcing agent and the polyepoxy compound and other suitable additives may be blended and the blend extruded and comminuted into pellets or other convenient form. The composition thus prepared is suitable as a molding composition in a variety of thenmoplastic processes. The following examples illustrate the preparation of compositions within the scope of the present invention. These examples are not to be construed to in any way limit the invention but rather to demonstrate its operability.
The advantages associated with the composition of the invention are attained without resorting to any other additives such as the sulfonate salts or sulfate salts that are disclosed in European Patent Application 10,773.
Mo-2391 i .
~L2 - lla -EXAMPT.ES
Compositions according to the invention nomlnally comprising 70 parts by weight (pbw) of poly(ethylene terephthalate) having an intrinsic Mo-2391 ~ `3 viscosity of about 0.6 dl/gm, a commercial product of Eastman Kodak available under the tracle name of TENITE*
7741~ and 30 pbw of glass fibers (PPG 3540) were prepared and ~ested as shown below. The dependence of the properties on the amount of the polyepoxy added to the compositions is apparent upon a comparison with the control (E~ample l-l) where~o no epoxide was added. In addition to the major c:omponents noted above, the compositions all contained minor amounts of a crystallization rate promoter, a nucleating agent and thermal and hydrolytic stabilizers in accordance ~ith U. S. Patent 4,223,113.
The polyepoxy resin (EPON* 1031) was mîxed into the molten composition by extrusion compounding. The e~truder, a two stage, single screw (2.75:1) equipped with vacuum vent ~etween stages was operated at 65 rpm at a temperature profile of 280/280/270/260/245/275C
(r -~ f).
Component/TextUnit 1~ 2 1-3 1-4 1-5 EPON 1031 conc'n ~ 0 .1 .2 .3 .5 IZOD, l/8 NotchJ/M 79 80 86 97 86 IZOD, 1/8 UnnotchJ/M 660 790550 980 770 25 Tensile @ BreakMPa 129 141147 152 151 Tenslle Retention(l) % 67 86 90 87 93 Flexural ModulusGPa 9.9 9.310.3 9.9 9.9 Flexural StrengthMPa 186 224232 240 _ 225 (l)After ageing, 8 hours at 121C in saturated steam.
*Trademark Mo-2391 , An improvement in the mechanical properties associated with flddltion of polyepoxide is demonstratet]
below t~ be substa~tially independent of the crystallization rate of polv(ethylene terephthalate).
The compositions all nominally based on 70 pbw of PET
(TENITE 7741~ and 30 pbw of glass fibers (PPG 3540~ were prepared by the same procedure described in Example 1 above. The repor~ed values represent averages of several experimental results obtained under generally similar conditions.
Component/Test Unit 2-1 2-2 2-3 2-4 Glass fibers ~ 30 30 30 30 15 Crystallization rate promoter(l) % 0 0 4.9 4.9 Polyepoxy(4) % 0 0.30 0 0.30 Izod N(2) 1/8 J/M 96.8 97 90 98.2 Izod UNN(3) 1/8 J/M 979 989 726 860 Tensile @ Break MPa 148 163 138 151 Aged 16 hr. 410F MPa 96 127 93 125 Flexural Modulus GPa 10.1 10.2 9.8 10 Flexural Strength MPa 230 254 205 234 (1) Polyhexane diol adipate (MW ahout 2000) (2) Notched specimens (3) Unnotched specimens ~4) Epon 103 * Trademark Mo-2391 EXAMPE _3 The compositions which properties are compared below were pr~pared in accordance with the procedure outlined above in Example 1 and are indicated to further demonstrate the efficacy of the polyepoxide additive in the present context. The polyester component used was TENITE 7741.. Polyhexane diol adipate, a crystallization rate promoter at a level of 4.9% was added to each of the compositions.
Component/TestUnit3-1 3-2 3-3 3-4 Conc'n 419AA(1) 41gAA(1) 3540(2) 3540( ) Conc'n % 30 30 30 30 EPON 1031 conc'n % 0 0.3 0 3 IZOD, 1/8 NotchJ/M102 105 79 89 IZOD9 1/8 Unnotch J/M 640 400 660 800 Tensile @ Break MPa135 141 130 152 Elong'n % 2 3 2 2 Flexural Stren~th MPa 197 212 193 235 (l)A product of Owens Corning Fiberglas Corp.
(2)A product of PPG, Inc.
Mo-2391 The series of experiments summarized in Table 4 demonstrates the efficacv of the polyepoxy compounds of the invention in imparting desirable mechanical properties to glass reinforced thermoplastic polyesters and compares these with the corresponding properties of the compositions modified with polyepoxides outside the present scope. Following the same preparation procedure as outlined above, the compositions were prepared, tested and evaluated as below. The compositions all comprised nominally, 70 pbw of PET (TENITE* 7741), 30 pbw of glass fiber (PPG* 3540) and about 4.9% of polyhexane diol adipate (~ about 2000) as a crystallization rate promoter.
Mo-2391 L ~D ~ ~
TA~LE 4 .
C~onent/ 4~1 4-2 4-3 4-4 4-5 4-6 4-7 Test Unit Intern~es ~lone 'l~ EPOXIDES
Epoxide EunctionalityNo. 2 4 5 none 1 2 4 EE~oxide Type(13 _ A B C -- X Y Z
Epoxide conc'n % 0.5 0.5 0.5 0 0.6 0.5 0.3 IZOD, 1/8 No~ch J/M 71 71 71 79 94 87 89 IZOD,1/8 Unnotch J/M460 510 540 660 480 470 800 10 Tensile @ Break MPa 136 138 141 130 95 142 . 152 Tensile Petention(2) % 80 84 88 67 78 92 89 Flex~ral Strenath MPa 198 200 208 190 168 231 235 15 (l)A = Epox~dized butyl ester of linseed oil B - EFoxidized soy bean oil C = Epoxidized linseed oil X = Phenyl glycidyl ether Y = EPA~Epichlor~hydrin reac~ion product 20 Z = Ethanediylidenetetrakis~4,1-phenyleneo~y methoxy)tetrakis-oxirane, homopolymer (2)After agemg 8 hours at 121C in saturated ste~n Mo-2391 Table 4 compares the efficacy of polyepoxides containing internal oxirane groupings such as those oE epoxidi~ed vegetable oils with polyepoxides containing terminal oxiranes such as those found in EPON 1031 with the reaction products of epichloro-hydrin with BPA. The table indicates:
a) ~ comparison of 4-5 with 4-4 shows that a terminal monoepoxide is not only not strength enhancing but is actually deleterious to strength development in the model reinforced, crystallizable P~T formulation.
b) The series 4-1 through 4-3 and 4-5 through 4 7 show that the action of the epoxide function in improving the strenyth and ductility of reinforced P~T is roughly proportional to the number of epoxides in the molecule~ Of particular importance in light of prior art, is the comparison of 4-7 with 4-6 which shows the significantly improved ductility and strength resulting from use of a tetrafunctional epoxide such as EPON 1031 as compared with the model composition modified with the difunctional epichlorohydrin/~P~ type epoxy re~in.
c~ The contrasts of 4-6 with 4-1 and 4-7 with 4-2 indicate that the terminal epoxides, particularly the terminal epoxides of the resins disclosed in this invention are significantly more efficient than internal epoxides such as those shown in the example and disclosed in U.S. Patent 3,886,104.
The epoxide in accordance with the inventionis shown upon comparing the properties of the composition of Example 5 to act as a coupling agent in the system of poly(alkylene terephthalate) glass Mo-2391 '~2~ 6 - 18 ~
reinforcementO The polyester and glass ,were as in Example 1 and the preparation of the compositions was in accorda~ce with the procedure outlined there.
A~;[E
5Component/Test Unit _ 5-1 5-2 5-3 Glass type(l) _861X10(3)861X10( ) 861X10( treatedsized EEON 1031 Conc'n ~ 0 0.15 0.15 IZOD 1/8 Notched J/M 52 74 62 10 IZOD 1/8 Unnotched J/M 370 640 420 Tensile @ ~ailure MPa 99 128 118 Flexural Mcdulus Gæa 8.8 9.6 9.3 Flexural Strength MPa 130 190 178 HD~ 264 psi C 1?2 216 _ 215 (1)861X10 is a glass oDntaining no organic material on its surface (2)861X10 treated with EPCN 1031 in a solvent, then heat-treated to drive off the solvent and ccmplete the SiOH/oxirane reaction.
(3)861X10 treated as in (2) but without the EPCN 1031.
(4)861X10 was dried at 220F overni~ht. EPON 1031 was added as a bulk additive.
Mo-2391 The preferred glass fibers in the context of the invention are PPG 3540* which are availabl,e from PPG
and which relevant sizing technology has been disclosed in U.S. Patent 4,271,229 issued June 2, 1981, Basically, these glass fibers are sized ~with a composition comprising thermoplastic, predominant]y aliphatic, curable polyurethane lattices, certain silane coupling agents and a lubricant system. The silane is understood to be one or more ureidofunctional silanes and one or more aminofunctional silanes.
*Trademark ~o-2391
Mo-2391 The preferred glass fibers in the context of the invention are PPG 3540* which are availabl,e from PPG
and which relevant sizing technology has been disclosed in U.S. Patent 4,271,229 issued June 2, 1981, Basically, these glass fibers are sized ~with a composition comprising thermoplastic, predominant]y aliphatic, curable polyurethane lattices, certain silane coupling agents and a lubricant system. The silane is understood to be one or more ureidofunctional silanes and one or more aminofunctional silanes.
*Trademark ~o-2391
Claims (13)
1. A thermoplastic molding composition comprising (i) a high molecular weight polyethylene terephthalate having an intrinsic viscosity of at least 0.4 dl/gm (ii) about 5 to 50 pbw of a reinforcing agent, (iii) about 0.05 to 5 pbw of a polyepoxy compound having three to five terminal epoxy functionalities per molecule, and (iv) a crystallization rate promoter.
2. The composition of Claim 1 wherein said (iii) is present in an amount of about 0.08 to about 1.0 pbw relative to the total weight of said (i) and said (ii).
3. The composition of Claim 1 wherein said (iii) is present in an amount of about 0.1 to about 0.8 pbw relative to the total weight of said (i) and said (ii).
4. The composition of Claim 1 or 2 or 3 wherein said reinforcing agent is glass fibers.
5. The composition of Claim 1 or 2 or 3 wherein said reinforcing agent is a combination of mica and glass fibers.
6. The composition of Claim 1 wherein said (iii) conforms to the general formula (II) wherein R1 denotes a hydrogen atom or an alkyl radical and R2 is a monovalent radical containing more than one additional terminal epoxide functionalities.
7. The composition of Claim 1 wherein said crystallization promoter is an oligomeric polyester.
8. A process for the preparation of a glass fiber reinforced thermoplastic polyester composition comprising applying about 0.05 to 5 percent of a polyepoxy compound having 3 to 5 terminal epoxy functionalities per molecule to said glass fibers, characterized in that said polyester has an intrinsic viscosity of at least 0.4 dl/gm and in that it is derived from dicarboxylic acids of which at least 85%
are aromatic, said composition being further characterized in that it contains a crystallization rate promoter.
are aromatic, said composition being further characterized in that it contains a crystallization rate promoter.
9. The composition of Claim 1 wherein said polyepoxy compound conforms to (III) where R is a C1-C4 alkylene, R3 is a polyvalent radical having a valence of n and n is an integer of at least 3.
10. A thermoplastic molding composition comprising (i) a high molecular weight polyethylene terephthalate having an intrinsic viscosity of 0.4 to 1.4 gm/dl as measured in a 1% solution of phenol and tetrachloroethane (60:40) at 25°C, (ii) about 10 to about 50 percent by weight of glass fibers, (iii) about 0.05 to about 5.0 percent by weight of a polyepoxy compound conforming to where R is a C1-C4 alkylene, R3 is a polyvalent radical having a valence of n and n is an integer of at least 3, and (iv) about 0.5 to about 30 percent of a crystallization rate promoter comprising structural units conforming to wherein R1 denotes a linear or branched aliphatic, cycloaliphatic or araliphatic divalent radical of 2-20 carbon atoms, R2 denotes a linear or branched aliphatic, cycloaliphatic, araliphatic or aromatic divalent radical of 2-20 carbon atoms, x denotes an integer of at least 2 and up to any value provided that the number average molecular weight of the oligomer is 600 to 3000, and y is an integer of 0 or 1.
11. A thermoplastic molding composition comprising (i) a high molecular weight polyethylene terephthalate, having an intrinsic viscosity of at least 0.4 dl/gm (ii) reinforcing glass fibers which are characterized in that they are sized with a second composition which comprises thermoplastic, predominantly aliphatic, curable polyurethane lattices, a silane coupling agent selected from among the group consisting of a ureidofunctional silane and an aminofunctional silane and a lubricating system, (iii) a polyepoxy compound having three to five terminal epoxy functionalities per molecule, and (iv) a crystallization rate promoter.
12. The thermoplastic composition of Claim 11 wherein said (iii) conforms to the general formula (II) wherein R1 denotes a hydrogen atom or an alkyl radical and R2 is a monovalent radical containing more than one additional terminal epoxide functionalities.
13. A thermoplastic molding composition comprising (i) a high molecular weight polyethylene terephthalate having an intrinsic viscosity of 0.4 to 1.4 gm/dl as measured in a 1% solution of phenol and tetrachlorethane (60:40) at 25°C, (ii) reinforcing glass fibers which are characterized in that they are sized with a second composition which comprises thermoplastic, predominantly aliphatic, curable polyurethane lattices, as silane coupling agents selected from among ureidofunctional silanes and aminofunctional silanes and a lubricating system, (iii) about 0.05 to about 5.0 percent by weight of a polyepoxy compound conforming to wherein R is a C1-C4 alkylene, R3 is a polyvalent radical having a valence of n and n is an integer of at least 3, and (iv) about 0.5 to about 30 percent of a crystallization rate promoter comprising structural units conforming to wherein R1 denotes a linear or branched aliphatic, cycloaliphatic or araliphatic divalent radical of 2-20 carbon atoms, R2 denotes a linear or branched aliphatic, cycloaliphatic, araliphatic or aromatic divalent radical of 2-20 carbon atoms, x denotes an integer of at least 2 and up to any value provided that the number average molecular weight of the oligomer is 600 to 3000, and y is an integer of 0 or 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US392,846 | 1982-06-28 | ||
| US06/392,846 US4533679A (en) | 1982-06-28 | 1982-06-28 | Reinforced polyester composition having an improved strength |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1240436A true CA1240436A (en) | 1988-08-09 |
Family
ID=23552247
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000427497A Expired CA1240436A (en) | 1982-06-28 | 1983-05-05 | Reinforced polyester composition having an improved strength |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4533679A (en) |
| EP (1) | EP0097870B1 (en) |
| JP (1) | JPS598750A (en) |
| CA (1) | CA1240436A (en) |
| DE (1) | DE3374690D1 (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2165253A (en) * | 1984-10-01 | 1986-04-09 | Mobay Chemical Corp | Glass fiber reinforced polycarbonates |
| US5030680A (en) * | 1988-04-05 | 1991-07-09 | Phillips Petroleum Company | Rapidly crystallizing polyethylene terephthalate blends |
| US5047450A (en) * | 1988-04-05 | 1991-09-10 | Phillips Petroleum Company | Polyethylene terephthalate molding resin blends |
| US5041476A (en) * | 1988-04-05 | 1991-08-20 | Phillips Petroleum Company | Rapidly crystallizing polyethylene terephthalate blends |
| ES2077077T3 (en) * | 1989-10-23 | 1995-11-16 | Eastman Chem Co | POLY (1,4-CYCLOHEXYLENDYMETHYLENE TEREFTALATE) WITH IMPROVED STABILITY IN MELTING. |
| WO1993002114A1 (en) * | 1991-07-18 | 1993-02-04 | General Electric Company | Stabilization of polyesters using epoxy compounds in combination with a catalyst |
| AU659196B2 (en) * | 1991-07-18 | 1995-05-11 | General Electric Company | Stabilization of mineral filled polyesters using epoxy compounds |
| JPH0616911A (en) * | 1992-06-30 | 1994-01-25 | Toray Ind Inc | Polyester resin composition |
| US5354791A (en) * | 1993-10-19 | 1994-10-11 | General Electric Company | Epoxy-functional polyester, polycarbonate with metal phosphate |
| ES2131620T3 (en) * | 1994-11-19 | 1999-08-01 | Gen Electric | POLYESTER RESINS REINFORCED WITH HYDROLYTICALLY STABLE FIBERGLASS. |
| US5877240A (en) * | 1997-09-26 | 1999-03-02 | Owens Corning Fiberglas Technology, Inc. | Sizing composition for glass fibers for reinforcement of engineered thermoplastic materials |
| US6277905B1 (en) | 1999-09-23 | 2001-08-21 | Eastman Chemical Company | Process for improving the toughness of PCT formulations by adding rubber impact modifiers |
| US20050245646A1 (en) * | 2000-12-26 | 2005-11-03 | Yoshihiro Ohtsuka | Thermoplastic polyester resin composition excellent in processing stability and molded articles thereof |
| US8048935B2 (en) * | 2004-11-08 | 2011-11-01 | Carpenter Co. | Liquid foam systems and ASTM E-84 class 1 rated rigid, high-density polyurethane foams and articles prepared therefrom |
| US20060100330A1 (en) * | 2004-11-10 | 2006-05-11 | Natarajan Kavilipalayam M | Composition for use in forming an article |
| US7375167B2 (en) * | 2005-05-09 | 2008-05-20 | Basf Se | Hydrolysis-resistance composition |
Family Cites Families (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3368995A (en) * | 1965-08-03 | 1968-02-13 | Teijin Ltd | Fiberglass reinforced polyethylene terephthalate |
| DE1694296C3 (en) * | 1966-10-08 | 1974-07-18 | Enka Glanzstoff Ag, 5600 Wuppertal | Manufacture of dimensionally stable and impact-resistant injection molded parts from polyethylene terephthalate mixtures |
| DE1769224C3 (en) * | 1968-04-23 | 1981-04-02 | Hoechst Ag, 6000 Frankfurt | Production of rapidly crystallizing molding compounds based on saturated polyester |
| DE1769230A1 (en) * | 1968-04-24 | 1972-03-02 | Hoechst Ag | Molding compositions containing thermoplastic polyesters |
| DE1769729A1 (en) * | 1968-07-04 | 1972-01-27 | Hoechst Ag | Molding composition containing thermoplastic polyester |
| BE755317A (en) * | 1969-08-29 | 1971-02-26 | Celanese Corp | MOLDING RESIN AND ITS PRODUCTION PROCESS |
| CH549614A (en) * | 1969-10-30 | 1974-05-31 | Hoechst Ag | Polyester injection mouldings |
| DE2124336C3 (en) * | 1971-05-17 | 1986-07-31 | Hoechst Ag, 6230 Frankfurt | Thermoplastic polyester molding compounds |
| BE794029A (en) * | 1972-02-28 | 1973-05-02 | Du Pont | THERMOPLASTIC COPOLYESTERS WITH SEGMENTS MODIFIED BY POLYEPOXIDES |
| US3886104A (en) * | 1973-01-05 | 1975-05-27 | Gen Electric | Stabilized polyester compositions |
| US4020122A (en) * | 1973-01-05 | 1977-04-26 | General Electric Company | Process for the preparation of polyester compositions having increased melt elasticity |
| JPS5222653B2 (en) * | 1973-07-11 | 1977-06-18 | ||
| JPS592707B2 (en) * | 1976-09-29 | 1984-01-20 | 三菱レイヨン株式会社 | polyester composition |
| US4223125A (en) * | 1976-11-23 | 1980-09-16 | Bayer Aktiengesellschaft | Polyester compositions which crystallize rapidly |
| US4123415A (en) * | 1976-12-06 | 1978-10-31 | General Electric Company | Reinforced thermoplastic polyester compositions having improved resistance to heat deflection |
| US4222928A (en) * | 1977-11-09 | 1980-09-16 | Teijin Limited | Polyester composition |
| SE430169C (en) * | 1978-02-28 | 1985-04-14 | Du Pont | SUBSTANCE PACKAGING PLASTIC COMPOSITION CONTAINING REINFORCEMENT OR FILLER AND USE OF IT |
| SE430168B (en) * | 1978-02-28 | 1983-10-24 | Du Pont | SUBSTANCE PACKAGING PLASTIC COMPOSITION CONTAINING REINFORCEMENT OR FILLER AND USE OF IT |
| JPS5910698B2 (en) * | 1978-05-18 | 1984-03-10 | 東洋紡績株式会社 | polyester composition |
| DE2834032A1 (en) * | 1978-08-03 | 1980-02-28 | Basf Ag | STABILIZED POLYALKYLENE TEREPHTHALATE MOLDING COMPOUNDS |
| JPS5592758A (en) * | 1978-11-06 | 1980-07-14 | Toray Ind Inc | Resin composition |
| US4212791A (en) * | 1979-02-23 | 1980-07-15 | Rohm And Haas | Poly(alkyleneterephthalate) molding compositions containing oligomeric polyester and segmented copolyester-polyether elastomer |
| JPS55131045A (en) * | 1979-03-31 | 1980-10-11 | Dainippon Ink & Chem Inc | Noncombustible resin composition |
| JPS5645928A (en) * | 1979-09-21 | 1981-04-25 | Teijin Ltd | Production of polyester extruded expanded article |
| JPS56155241A (en) * | 1980-05-01 | 1981-12-01 | Teijin Ltd | Flame-retardant polyester resin |
| JPS5792044A (en) * | 1980-11-28 | 1982-06-08 | Toray Ind Inc | Thermoplastic polyester composition |
| MX2007000135A (en) * | 2004-06-30 | 2007-03-07 | Johnson & Son Inc S C | Improved wick to reduce liquid flooding and control release rate. |
-
1982
- 1982-06-28 US US06/392,846 patent/US4533679A/en not_active Expired - Fee Related
-
1983
- 1983-05-05 CA CA000427497A patent/CA1240436A/en not_active Expired
- 1983-06-15 EP EP83105840A patent/EP0097870B1/en not_active Expired
- 1983-06-15 DE DE8383105840T patent/DE3374690D1/en not_active Expired
- 1983-06-23 JP JP58111978A patent/JPS598750A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| DE3374690D1 (en) | 1988-01-07 |
| EP0097870A1 (en) | 1984-01-11 |
| JPS598750A (en) | 1984-01-18 |
| EP0097870B1 (en) | 1987-11-25 |
| US4533679A (en) | 1985-08-06 |
| JPH0160179B2 (en) | 1989-12-21 |
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| MKEX | Expiry |