|Publication number||US4540729 A|
|Application number||US 06/650,082|
|Publication date||Sep 10, 1985|
|Filing date||Sep 13, 1984|
|Priority date||Sep 16, 1983|
|Also published as||DE3433852A1|
|Publication number||06650082, 650082, US 4540729 A, US 4540729A, US-A-4540729, US4540729 A, US4540729A|
|Inventors||Richard S. Williams|
|Original Assignee||Bip Chemicals Limited|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (9), Referenced by (25), Classifications (16), Legal Events (4)|
|External Links: USPTO, USPTO Assignment, Espacenet|
The invention relates to polyester compositions, particularly those based on polyethylene terephthalate (PET).
The combination of PET with high molecular weight polycaprolactone and suitable nucleants as described in our UK patent application No. 83 19627 gives a moulding material with superior mould release and lower mould temperature requirements and also superior impact strength, particularly in glass fibre filled compositions. Further reductions in the mould temperature required for glossy mouldings can be achieved by the addition of suitable plasticizers but these generally cause a drop in the impact strength. For instance, dibenzyl adipate, dibenzyl azelate, neopentyl glycol dibenzoate and polyethylene glycols all act as suitable plasticizers lowering mould temperature for glossy mouldings but they all reduce the impact strength of the moulding so produced.
Thus it is highly desirable to find a means of lowering the mould temperature required without an accompanying penalty in loss of impact strength.
EP No. 073 042 discloses the use of epoxidised plasticizers in improving the moulding capacity of PET compositions and suggests that they have a synergistic effect with some nucleants, including sodium stearate. There is no discussion in this specification concerning impact strengths, and no disclosure of use of polycaprolactones.
According to the present invention a polyester moulding composition comprises polyethylene terephthalate or a polyester containing at least 80% of polyethylene terephthalate repeating units, polycaprolactone having a number average molecular weight of above 10,000, a nucleant for crystallization of the polyethylene terephthalate and an epoxidised unsaturated triglyceride containing at least one epoxide group.
The epoxidised unsaturated triglyceride functions as a plasticizer to improve the mouldability of the composition but we have found that when used in these compositions in conjunction with the high molecular weight polycaprolactone these compounds further improve the impact strength of the composition, an effect opposite to that normally produced by such use of plasticizer.
The epoxidised unsaturated triglyceride may be an individual compound or mixture of compounds. Examples of unsaturated triglycerides which may be epoxidised include linseed oil, soybean oil, sunflower seed oil, safflower oil, hempseed oil, tung oil, oiticica oil, corn oil, sesame oil, cottonseed oil, castor oil, olive oil, peanut oil, rapeseed oil, coconut oil, babassu oil, palm oil and the like.
It is preferable that the epoxidised unsaturated triglyceride should be relatively non-volatile because of the processing conditions used to compound the PET composition. Perferably the molecular weight of the epoxidised unsaturated triglyceride is at least 400.
The particularly preferred triglyceride is mono-epoxidised soybean oil.
The composition may contain a reinforcing fibre, for example short lengths of reinforcing fibre such as glass fibre, although other types of fibre which will stand up to the processing conditions to which the composition is subjected may be used.
The nucleant may be either a metal salt of an organic acid, for example a metal stearate, acetate or benzoate, or a finely divided material which does not melt at or below the melting point of polyethylene terephthalate, for example microtalc. The preferred nucleant is a group 1 metal stearate, or microtalc with a particle size of less less 20 microns.
Preferably the group I metal stearate is sodium stearate, which is a known nucleant for polyethylene terephthalate and gives easier nucleation of the polyester. The nucleant is preferably used in an amount no more than 1% by weight of the composition, particularly in the range 0.1 to 0.7% by weight. However, if a finely divided solid nucleant is used it may be used in greater proportion, eg up to six parts by weight per 100 parts by weight total polymer, and may be used, if desired, in addition to a nucleant of the other type.
The polycaprolactone is an aliphatic polyester which has a repeat unit of --CO--(CH2)5 --0--n, the end groups depending upon the initiator used to start polymerisation of the caprolactone. In the present invention, the caprolactone polymers have a number average molecular weight above 10,000, for example in the range 10,000 to 300,000.
Preferably the polycaprolactones have a number average (N A) Molecular weight of at least 20,500 and preferably also a N A molecular weight not greater than 100,000.
The amount of the polycaprolactone in the composition will generally be at least 2.5 parts by weight per 100 parts by weight total polymer and may, if desired, be substantial e.g. up to 25 parts by weight per 100 parts by weight total polymer. (By `total polymer` in this specification we mean the total of polyethylene terephthalate based polyster plus the higher molecular weight polycaprolactone).
The total amount of epoxidised unsaturated triglyceride used as plasticizer will not generally be more than 10 parts by weight per 100 parts by weight of total polymer and preferably is in the range 1 to 6 parts by weight per 100 parts by weight of total polymer.
The invention will now be described more particularly by means of examples.
In these examples the following are the materials which were used in the various compositions:
______________________________________Fibre Grade Polyethylene Terephthalate PET (FG) (from Courtaulds).Bottle Grade " PET (BG) (Melinar B90' from ICI)______________________________________
Glass Fibre (ECO 680 3 mm chopped strand from T-Glass Fibres Limited)
Polycaprolactone--CAPA 601P (NA molecular weight 47,000 from Interox Chemicals Ltd)
Epoxidised Soybean oil--Drapex 6.8 (from Argus Chemical Corporation)
Epoxidised Soybean oil--Estabex 2307 (from AKZO Chemie)
Neopentyl glycol dibenzoate (NPGDB)
In each example all the ingredients of the composition were mixed together and then compounded on a twin screw (Welding Engineers) extruder. The amounts of glass fibre are quoted as percentages by weight of the total composition.
These examples show the effect of adding two different plasticizers to a PET composition containing 90 parts by weight of PET (FG), 10 parts by weight of CAPA 601P, 0.5 parts by weight sodium stearate, and 20% glass fibre. The type and amount of plasticizer used and the physical properties of test mouldings made from the compositions are given below in Table 1*.
TABLE 1______________________________________Example No 1 2 3______________________________________Plasticizer Type -- Drapex 6.8 NPGDBPts Wt Plasticizer -- 3 3Tensile Strength MPa 91 95 73Tensile Modulus GPa 6.3 6.7 7.1Flexural Strength MPa 134 154 136Flexural Modulus GPa 6.5 6.3 6.6CNIS KJ/m2 6.9 9.2 5.4CUIS KJ/m2 25 30 15______________________________________
These examples show the effect of the plasticizer Estabex 2307 in compositions with polycaprolactone. The basic composition in each Example was 90 parts by wt PET (FG) and 0.5 parts by wt of sodium stearate, with 20% glass fibre. Details are given below in Table 2*.
TABLE 2______________________________________Example No 4 5 6______________________________________Pts CAPA 601P -- 10 10Pts Estabex 3 -- 3Tensile Strength MPa 99 76 88Tensile Modulus GPa 7.8 7.0 7.3Flexural Strength MPa 164 122 136Flexural Modulus GPa 6.7 5.8 5.5CNIS KJ/m2 5.4 5.5 10.2CUIS KJ/M2 20 16 27______________________________________
It will be noted that the impact strength in Example 6 is markedly improved over that in both Examples 4 and 5, showing the value of combining the polycaprolactone and the epoxidised soybean oil.
These examples are similar 4 to 6 except that a 30% glass level was used in the compositions. Details are given below in Table 3*.
TABLE 3______________________________________Example No 7 8 9______________________________________Pts CAPA 601P -- 10 10Pts Estabex 3 -- 3Tensile Strength MPa 133 105 111Tensile Modulus GPa 11.0 9.0 9.4Flexural Strength MPa 189 162 164Flexural Modulus GPa 9.2 8.2 8.1CNIS KJ/m2 8.0 8.3 12.5CUIS KJ/m2 26 25 47______________________________________
It will be noted that here again is marked improvement in impact strength in the use of two additives in conjunction.
These examples show the use of the epoxidised soybean oil in a bottle grade PET. In these examples the basic composition was 90 parts by wt PET (BG), 10 parts by wt of CAPA 601P and 0.5 parts by wt of sodium stearate with 15% of glass fibre. A marked improvement in the unnotched impact strength only is obtained in this case. Details are given below in Table 4*.
TABLE IV______________________________________Example No 10 11______________________________________Pts Estabex -- 3Pts CAPA 601P 10 10Tensile Strength MPa 74 78Tensile Modulus GPa 5.2 6.1Flexural Strength MPa 129 127Flexural Modulus GPa 4.6 4.8CNIS KJ/m2 12.2 11.6CUIS KJ/M2 21 37______________________________________
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|U.S. Classification||524/114, 525/411, 524/539, 260/DIG.350|
|International Classification||C08L63/00, C08K5/1515, C08L67/04, C08L67/02, C08K5/09, C08L67/00, C08K5/00|
|Cooperative Classification||Y10S260/35, C08L67/02, C08K5/1515|
|European Classification||C08K5/1515, C08L67/02|
|Sep 13, 1984||AS||Assignment|
Owner name: BIP CHEMICALS LIMITED 20 ST. MARY S PARSONAGE, MAN
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:WILLIAMS, RICHARD S.;REEL/FRAME:004315/0102
Effective date: 19840830
Owner name: BIP CHEMICALS LIMITED A CORP. OF GREAT BRITAIN,ENG
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:WILLIAMS, RICHARD S.;REEL/FRAME:004315/0102
Effective date: 19840830
|Mar 2, 1989||FPAY||Fee payment|
Year of fee payment: 4
|Sep 12, 1993||LAPS||Lapse for failure to pay maintenance fees|
|Nov 30, 1993||FP||Expired due to failure to pay maintenance fee|
Effective date: 19930912