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WO1993008231A1 - Melanges de polymeres - Google Patents

Melanges de polymeres Download PDF

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Publication number
WO1993008231A1
WO1993008231A1 PCT/GB1992/001912 GB9201912W WO9308231A1 WO 1993008231 A1 WO1993008231 A1 WO 1993008231A1 GB 9201912 W GB9201912 W GB 9201912W WO 9308231 A1 WO9308231 A1 WO 9308231A1
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WO
WIPO (PCT)
Prior art keywords
liquid crystal
crystal material
polymer blend
acid
polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/GB1992/001912
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English (en)
Inventor
Paul Thomas Alder
John Groves Dolden
David George Othen
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BP PLC
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BP PLC
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Filing date
Publication date
Application filed by BP PLC filed Critical BP PLC
Publication of WO1993008231A1 publication Critical patent/WO1993008231A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • 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

Definitions

  • the present invention relates to blends of thermoplastic polymers having improved melt processability.
  • EP 30417 discloses melt processable compositions having improved processability which comprise blends of two thermoplastic polymers, at least one of which is capable of forming an anisotropic melt.
  • the formation of an anisotropic melt is a characteristic of a liquid crystal and polymers producing such melts may be termed "liquid crystal polymers".
  • polymers which are mentioned as one component of the blend are polyolefines.
  • specific polyolefines mentioned are polypropylene and low density polyethylene.
  • polymers forming anisotropic melts which may be used as the other components of polymer " blends are polyesters described in GB1,507,207, US3,778,410, US4,067,852, US4,083,829, US4,130,545, and US4,161,470.
  • specific polymers exemplified are liquid crystal polymers derived from reactions of various derivatives of aromatic hydroxyl acids and long chain alkanedioic acids or dihydroxy compounds.
  • Japanese published unexamined application JP-01036653A discloses blends of an ultra high molecular weight polyethylene with a polymer giving an anisotropic melt.
  • the polymers forming anisotropic melts include copolymers of polyethylene terephthalate and p-hydroxybenzoic acid, together with copolymers of p- hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid.
  • a polymer blend comprising polyethylene and a liquid crystal material
  • the liquid crystal material is a random copolymer of: a) an aliphatic dicarboxylic acid in which the carboxylic acid groups are linked by a chain containing x carbon atoms, b) a 1,4 dihydroxy benzene, and c) 4-hydroxybenzoic acid, wherein x is in the range 2 to 20, and the 4-hydroxybenzoic acid constitutes 10 to 90 mol % of the monomers from which the liquid crystal material is derived.
  • liquid crystal material In the preparation of the liquid crystal material it is preferred to use about equimolar amounts of dicarboxylic acid and 1,4-dihydroxy benzene, except when monofunctional molecular weight limiters are used as explained below.
  • the preferred liquid crystal materials are those in which x is 4 to 10.
  • the 4-hydroxybenzoic acid constitutes 10 to 50 mol% of the monomers used to make the liquid crystal material.
  • the liquid crystal material may optionally contain up to 20 mol% of a monofunctional carboxylic acid, e.g benzoic acid, as a molecular weight limiter.
  • a monofunctional carboxylic acid e.g benzoic acid
  • the quantity of aliphatic dicarboxylic acid may be reduced in order to provide equal numbers of carboxylic acid and hydroxy groups.
  • monofunctional phenols of low volatility may be used as molecular weight limiters.
  • Liquid crystal polymers suitable for use in the present invention are known. Liquid crystal polymers which may be used in the present invention may be described by formula:
  • a preferred polymer is that wherein a is p- hydroxybenzoic acid, b is hydroquinone and c is sebacic acid. If benzoic acid is present as a molecular weight limiter the preferred polymer is that wherein the mole fractions of components p- hydroxybenzoic acid, hydroquinone, sebacic acid are equal to 0.3, 0.35 and 0.35 respectively.
  • liquid crystal polymer When describing the liquid crystal polymer as a derivative of various acids and hydroxy compounds we do not intend to restrict the synthesis to starting materials which are in the form of the free acids or hydroxy compounds. Thus in some cases starting materials may be used containing an acyloxy group which reacts in a way equivalent to a hydroxy group.
  • the reaction may be carried out in a liquid medium in which the reactants are dispersed, together with a catalyst such as an alkali metal acetate.
  • a catalyst such as an alkali metal acetate.
  • High shear agitation may be desirable initially to disperse the reactants and subsequently to maintain the products dispersed as reaction proceeds.
  • the reaction is carried out at elevated temperatures, eg, 250° - 330°C, preferably 290° - 300°C.
  • a stream of inert gas is preferably passed through the reaction mixture to remove by-products.
  • Some polymerization starts to occur at about 240°C, but the reaction mixture is preferably heated to above 290°C, preferably as rapidly as is possible with the equipment used.
  • the duration of the polymerization step which may be defined as time at a temperature in excess of 290°C, may for example be in the range 60 to 120 minutes.
  • the liquid crystal polymer may be formed by melt polymerization. Melt polymerization may be carried out in two stages. The first stage is a gradual heating to the final polymerization temperature. In the second stage the reaction mixture is held at the polymerization temperature and subjected to a vacuum.
  • the present invention may be applied to a variety of polyethylenes. Thus it may be applied to HDPE (high density polyethylene), LDPE (low density polyethylene), and MDPE (medium density polyethylene). Polyethylenes may be characterized by their MFR (Melt Flow
  • MFR is the quantity of melt extruded in 10 minutes through a die of standard dimensions under a defined load at a defined temperature. The test is carried out in accordance with ISO 1133-1981 or BS 3412:1976.
  • the invention may be applied to any pol olefin where processing improvements are desirable, it is of most value for materials of MFR less than 0.3 (2.16 kg, 190°C), especially high molecular weight grades of MFR less than 10 (21.6 kg,190°C).
  • Blends of the polyethylene and liquid crystal polymer may be prepared by any of the polymer melt blending techniques known in the art, e.g. batch mixers and single-screw or twin-screw extruders.
  • the liquid crystal polymer may be blended with the polyethylene in an amount corresponding to 0.01 - 5% by weight of the total blend.
  • the addition of low levels of the liquid crystal materials to polyethylenes by twin screw extrusion compounding results in a reduction in melt viscosity with a reduction in temperature and specific energy during compounding.
  • Extrusion using single screw extruders to produce pipe, film or blow mouldings leads to reduced die head pressures without substantially damaging the properties of the product. This has the advantage of increased throughput during extrusion.
  • the polymer blends eliminate sharkskin which is a non-smooth surface texture due to melt flow instability and improve film appearance.
  • liquid crystal polymer used in the examples was synthesized by melt polymerization or by a dispersion polymerization process. Melt polymerization This method was used for Example 2 and comparative Tests B and C.
  • the polymerization was carried out in a cylindrical borosilicate glass reaction vessel with an air driven helical stirrer and fittings for distillation under inert gas or high vacuum.
  • the flask was heated in a fluidized bed of sand in an apparatus sold as Tecam SBL- 2, and capable of controlled heating above 350°C.
  • the apparatus was generally lagged to improve distillation rate.
  • the reactants containing hydroxy groups were reacted with acetic anhydride to convert the hydroxy groups to acetoxy groups before reaction.
  • a mixture of dried reactants were placed in the polymerization vessel and purged at least three times with dry nitrogen/high vacuum.
  • the reactants were further dried at 100-130°C for 45-60 minutes under a vacuum of 6.67-13.33 Pa (0.05-0.1mm Hg) .
  • the contents of the polymerization vessel were then sealed under nitrogen and the vessel was then removed from the heating bath.
  • the bath was then heated to a temperature of about 260-280°C unless otherwise stated (i.e. about 20°C below the desired polymerization temperature.
  • the vessel was then returned to the bath and stirring was commenced as soon as the monomers had melted.
  • the polymerization reaction involves the liberation of acetic acid and distillation under nitrogen was carried out until approximately 80% of the theoretical acetic acid had been evolved. During distillation the temperature of the bath was gradually increased to the required polymerization temperature (280- 300°C unless otherwise stated. Distillation under a vacuum of 26.66- 66.66 Pa (0.2-0.5 mm Hg)
  • the polymer was removed from the reaction vessel while hot. Dispersion process
  • the typical procedure was as follows:
  • the dispersing medium was a mixture of hydrogenated terphenyls, sold under the trade name Santotherm 66, used in a proportion of 1- 1.5rl w/w on acetylated monomers.
  • the dispersing medium was deoxygenated before use by purging overnight with nitrogen.
  • About 100 ml of the dispersing medium charge was reserved and the dispersion aid, an organo-functionalized montmorillonite clay sold under the trade name Bentone 34, (at 0.5-1.375% w/w on acetylated monomers) and catalyst (potassium acetate at 50-250 ppm on acetylated monomers) dispersed in it using a high speed disperser ("Silverson”) under nitrogen.
  • Bentone 34 an organo-functionalized montmorillonite clay sold under the trade name Bentone 34
  • the dry monomers were charged to a flanged flask equipped with a stainless steel stirrer, nitrogen purge tube, pressure equalised dropping funnel, heater control thermocouple, and switchable reflux/distillation condenser.
  • the apparatus was thoroughly purged with nitrogen (typically overnight), and a slow flow of gas through the apparatus maintained.
  • the reagents were acetylated by addition of acetic anhydride (5 mole % excess) and refluxing at 150°C for 45 min with slow stirring. The temperature was increased to 170°C and acetic acid and excess acetic anhydride distilled off. T e flow of nitrogen was then increased and the bulk of the Santotherm added, followed by the pre-dispersion. The stirrer speed was increased to about 1250 rpm to disperse the monomers and the temperature was then raised to 290-300 C. Acetic acid is collected as the polymerization proceeds. When the polymerization stage was complete the heater was switched off and the apparatus allowed to cool.
  • IVs Intrinsic Viscosities
  • a liquid crystal polymer was prepared as follows.
  • the reactants used were p-hydroxybenzoic acid, hydroquinone, sebacic acid and benzoic acid in the molar ratio of 0.3:0.35:0.325:0.05.
  • the reaction was carried out by dispersion polymerization as described above.
  • the resulting polymer had an Inherent Viscosity (determined as described above using 4-chlorophenol) of 0.18.
  • the polymer was shown to form a liquid crystal melt by observation of a birefringent mesophase using a polarizing microscope fitted with a hot stage.
  • the polymer was then used to form a blend with a high molecular weight high density polyethylene.
  • the polyethylene was a polymer commercially available under the trade name "Rigidex" HM5420XP. This was a high molecular weight HDPE blow-moulding grade. It had an MFR (21.6 kg) of 2 and a density of 0.954.
  • the blend was formed by dry mixing particles of the liquid crystal polymer with polyethylene powder in the desired proportions. It contained 5 % by weight of the liquid crystal polymer, based on the total weight of blend.
  • the blend was then fed to a "Brabender" PLE 651 drive with a W 30 roller mixer head and a quick loading chute.
  • the torque developed by the drive is related to the the viscosity of the melt under the shear conditions of the test.
  • the amount of blend fed was 30g.
  • the load on the chamber was 5 kg weight and the speed was 30 rp .
  • the chamber was heated to 200°C - 205°C and the charge of blend was added rapidly at low speed.
  • Speed was then increased to 30 rpm and the torque recorded against time.
  • the equilibrium torque is the value to which the torque tends once melting and mixing are complete. Equilibrium is generally assumed to have been reached when the torque is approximately constant over a ⁇ o minute period. The equilibrium value was found to be 10.8 Nm. Comparative Test A
  • Example 2 In a comparative test not according to the invention an equilibrium value of Brabender torque was determined as in Example 1 but without any liquid crystal polymer added to the high molecular weight high density polyethylene. The equilibrium torque was 16.5 Nm. A comparison of the equilibrium torques for Example 1 and Test A shows that the use of the liquid crystal polymer of the invention gave a considerable reduction in torque corresponding to a significant reduction in melt viscosity.
  • Example 2
  • a liquid crystal polymer of the type made in Example 1 was synthesized by melt polymerization using the proportions of starting materials given in Table 1. This also gives the time for which acetic acid was distilled off and the time for which the reactants were heated under vacuum after acetic acid had distilled off.
  • the polymer was blended and tested as in Example 1.
  • a liquid crystal polymer consisting of units derived from p-hydroxybenzoic acid and 2-hydroxy-6-naphthoic acid was synthesized by melt polymerization.
  • Examples 3 and 4 show the use of the liquid crystal polymers as process aids in polyethylene extrusion.
  • a liquid crystal polymer was prepared as described above from the following components: p-hydroxybenzoic acid 207.2g hydroquinone 192.7g sebacic acid 354g benzoic acid 10.7g
  • the polymerisation time (>290°C) was 100 min.
  • the liquid crystal polymer was blended with Rigidex HM4516AP, a resin used in pipe compounds supplied by BP Chemicals, according to the following procedure.
  • liquid crystal polymer HM4516AP powder and Irganox 1010 anti-oxidant were pre-blended in a Pappenmeier powder blender for 5 min at 700-800 rpm. Blends containing 0, 0.25, 0.5, 1.0 and 2.0% w/w of the liquid crystal polymer were produced.
  • blends were compounded using a Brabender DSK 42/7 contra- rotating twin-screw bench top extruder at 25 rpm and a 3mm round, conical entry die with the following process temperatures:
  • Heating Zone 1 2 3 Die Temperature °C : 170 185 200 205
  • the resulting strand was collected and pelletised using a Betol pelletiser.
  • Blend processability was then evaluated by extrusion through a Brabender 19/25D single-screw bench top extruder at a range of screw speeds typically 10, 20-25, 40-50 and 65-75 rpm.
  • the screw compression ratio was 3:1 and a 1.5mm round, conical entry die was used.
  • the processing temperatures were as for the compounding operations.
  • Both the die pressure and output were monitored and readings taken at regular intervals, generally three sets of readings at each screw speed.- Pressure readings were taken at the mid-point of the range observed over a 1 minute period.
  • liquid crystal polymers (A-E) were compounded with Rigidex HM5420XP using a 30mm intermeshing co-rotating twin screw extruder (Werner S Pfleiderer ZSK30), a Tron T-20 volumetric feeder and a Cumberland pelletiser.
  • the ZSK30 extruder had 8 barrel sections with 5 separate temperature control zones and melt pressure measurement at the die. A die plate with a single 5 mm hole was fitted.
  • liquid crystal polymer was blended with the HM5420XP powder in a tumble blender prior to extrusion.
  • the resultant pelletised blends were used to blow bottles on a Kautex KEB4 blow moulder fitted with a 50mm single screw.
  • the extruder barrel had a grooved feed zone and six separate temperature control zones along the barrel.
  • the machine was fitted with a low compression head and a diverging 11mm die with a 9mm mandrel. A 4oz. stress resistance bottle mould was used.
  • the temperature profile used in all blends was 170, 190, 210, 210, 220 and 230°C.
  • Innovex LL7206AA a film grade linear low density polyethylene supplied by BP Chemicals
  • the liquid crystal polymer and a standard antioxidant/stabiliser additive were powder blended and compounded on a Werner fi Pfleiderer ZSK30 twin-screw compounding extruder.
  • the additive comprised 0.03% w/w Irganox 1010, 0.1% w/w Irgaphos PEP Q and 0.1% w/w calcium stearate.
  • the following blends were prepared:
  • the heating zone temperatures used were as follows:
  • the liquid crystal polymers reduced the die pressure, machine torque and melt temperature.
  • the extruder blends were pelletised using an Accrapak 750/6 pelletiser.
  • the pelletised blends were extruded into film using a Betol BK32 32mm single screw film extruder with a die gap of 0.6mm and a screw speed of 80 rpm.
  • the heating zone temperatures during extrusion were 200/150/190/190/190/200 and 200°C (die).
  • Sharkskin is a surface defect due to melt flow instability on extrusion at high shear rate which reduces gloss and clarity of the film.
  • This example shows the reduction in die pressures observed during pipe extrusion of the liquid crystal polymer blends.
  • the additive consisted of:
  • Liquid crystal polymer levels of 0, 0.2, 0.5 and 2% were used for the tests.
  • the blends were produced on the 50Kg scale using a Werner £ Pfleiderer ZSK53 co-rotating twin screw extruder, pelletised and used to make pipe on a Davy 6.5 cm pipe extruder.
  • Figure 2 represents a plot of die pressure against output rate and shows a substantial reduction in die pressure for a given output. However this required an increase in screw speed to maintain output as may be expected for a true reduction in bulk viscosity.
  • Example 7
  • This example shows the rheological properties of the liquid crystal polymer blends described in Example 6.
  • Figures 3 and 4 represent plots of shear stress and viscosity respectively against shear rate and show a systematic drop in viscosity with increasing liquid crystal polymer content across the shear rate range examined.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Des mélanges de polymères se composent d'un polyéthylène et d'un polymère cristallin liquide d'un copolymère sans ordre comprenant: (a) un acide dicarboxylique aliphatique dans lequel les groupes d'acide carboxylique sont limités par une chaîne contenant x atomes de carbone, (b) un 1,4-dihydroxy benzène et (c) un acide 4-hydroxybenzoïque, x étant compris entre 2 et 20 et l'acide 4-hydroxybenzoïque constituant un pourcentage molaire compris entre 10 et 90 des monomères à partir desquels le matériau cristallin liquide est dérivé. Ces mélanges de polymères présentent une meilleure aptitude au traitement en fusion.
PCT/GB1992/001912 1991-10-22 1992-10-19 Melanges de polymeres Ceased WO1993008231A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB919122327A GB9122327D0 (en) 1991-10-22 1991-10-22 Polymer blends
GB9122327.1 1991-10-22

Publications (1)

Publication Number Publication Date
WO1993008231A1 true WO1993008231A1 (fr) 1993-04-29

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WO (1) WO1993008231A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997006210A1 (fr) * 1995-08-04 1997-02-20 Basf Aktiengesellschaft Matieres moulables thermoplastiques a base de polymeres d'ethylene et de polyesters thermoplastiques
CN1058276C (zh) * 1997-08-26 2000-11-08 国家建筑材料工业局玻璃钢研究设计院 注射团状模塑料
WO2006085051A1 (fr) * 2005-02-09 2006-08-17 Ineos Europe Limited Copolymères et films obtenus à partir de ces copolymères

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0030417B1 (fr) * 1979-11-30 1983-12-07 Imperial Chemical Industries Plc Compositions de polymères usinables à état liquide, ayant une usinabilité améliorée et procédé d'usinage
EP0340655A2 (fr) * 1988-05-02 1989-11-08 HIMONT ITALIA S.r.l. Compositions contenant des polymères thermiquement incompatibles

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0030417B1 (fr) * 1979-11-30 1983-12-07 Imperial Chemical Industries Plc Compositions de polymères usinables à état liquide, ayant une usinabilité améliorée et procédé d'usinage
EP0340655A2 (fr) * 1988-05-02 1989-11-08 HIMONT ITALIA S.r.l. Compositions contenant des polymères thermiquement incompatibles

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997006210A1 (fr) * 1995-08-04 1997-02-20 Basf Aktiengesellschaft Matieres moulables thermoplastiques a base de polymeres d'ethylene et de polyesters thermoplastiques
US6048937A (en) * 1995-08-04 2000-04-11 Basf Aktiengesellschaft Thermoplastic molding compounds based on ethylene polymers and thermoplastic polyesters
CN1058276C (zh) * 1997-08-26 2000-11-08 国家建筑材料工业局玻璃钢研究设计院 注射团状模塑料
WO2006085051A1 (fr) * 2005-02-09 2006-08-17 Ineos Europe Limited Copolymères et films obtenus à partir de ces copolymères
US7968659B2 (en) 2005-02-09 2011-06-28 Ineos Europe Limited Copolymers and films thereof

Also Published As

Publication number Publication date
GB9122327D0 (en) 1991-12-04

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