GB2048285A - Modified Polyester Compositions - Google Patents
Modified Polyester Compositions Download PDFInfo
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- GB2048285A GB2048285A GB7914500A GB7914500A GB2048285A GB 2048285 A GB2048285 A GB 2048285A GB 7914500 A GB7914500 A GB 7914500A GB 7914500 A GB7914500 A GB 7914500A GB 2048285 A GB2048285 A GB 2048285A
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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
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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
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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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
Modified thermoplastic polyester compositions are provided which comprise (a) a poly (1,4-butylene terephthalate) resin and, optionally, a poly(ethylene terephthalate) resin and (b) a modifier therefore comprising (i) a silane-treated clay; (ii) acicular calcium metasilicate, (iii) a combination of segmented copolyester and an aromatic polycarbonate; or (iv) novaculite or a combination thereof. The modifiers provide easier processability and enhanced resistance to warpage in articles molded from the compositions.
Description
SPECIFICATION
Modified Polyester Compositions
This invention relates to modified thermoplastic polyester compositions which are more readily moldable to articles of improved dimensional stability. More particularly, the invention pertains to compositions of a poly( 1 4-butylene terephthalate) resin and, optionally, a poly(ethylene terephthalate) resin which are modified with an effective amount of a mineral filler or a resinous combination.
Background of the Invention
High molecular weight linear polyesters and copolyesters of glycols and terephthalic or isophthalic acid have been available for a number of years. These are described inter alia in Whinfield et al. U.S.
2,465,319 and in Pengilly, U.S. 3,047,539, incorporated herein by reference. These patents disclose that the polyesters are particularly advantageous as film and fiber formers.
With the development of molecular weight control, the use of nucleating agents and two-step molding cycles, poly(ethylene terephthalate) has become an important constituent of injection moldable compositions. Poly( 1 ,4-butylene terephthalate), because of its very rapid crystallization from the melt, is uniquely useful as a component in such compositions. Workpieces molded from such polyester resins, in comparison with other thermoplastics, offer a high degree of surface hardness and abrasion resistance, high gloss, and lower surface friction.
Stable polyblends of poly(1 ,4-butylene terephthalate) and poly(ethylene terephthalate) can be unreinforced and reinforced and molded into useful articles. See Fox and Wambach., U.S. 3,953,394, incorporated herein by reference. It has now been discovered that such polyesters and polyblends can be greatly improved in processability and dimensional stability by intimately admixing therewith a select family of modifiers.
Description of the Invention
According to one aspect of this invention, there are provided thermoplastic compositions which are useful for molding, e.g., injection molding, compression molding, transfer molding, and the like, the compositions comprising:
(a) a polyester composition comprising, in intimate admixture, a poly( 1 ,4-butylene terephthalate) resin and a poly(ethylene terephthalate) resin and
(b) an amount of up to 60 parts per 100 parts by weight of (a) and (b) of a modifier therefor comprising:
(i) a silane-treated clay;
(ii) acicular calcium metasilicate
(iii) a combination of a segmented copolyester and an aromatic polycarbonate; or
(iv) novaculite, or a mixture thereof.
According to a second aspect of this invention, there are provided thermoplastic compositions comprising
(a) a poly(1 ,4-butylene terephthalate) and
(b) a modifier therefor comprising in combination
(v) an aminosilane-treated clay; and
(vi) a segmented copolyester.
The polyester resins of the compositions of this invention are available commercially or can be prepared by known techniques such as by the alcoholysis of esters of terephthalic acid with ethylene glycol or butane diol and subsequent polymerization, by heating the glycols with the free acids or with halide derivatives thereof, and similar processes. These are described in U.S. 2,465,319 and U.S.
3,047,539, and elsewhere.
Illustratively, these high molecular weight polyesters will have an intrinsic viscosity of at least about 0.4 deciliters/gram and preferably, at least 0.6 deciliters/gram as measured in a 60:40 phenol/tetrachloroethane mixture at 30 C.
Especially useful when high melt strength is important are branched high melt viscosity poly(1 ,4- butylene terephthalate) resins, which include a small amount, e.g., up to 5 mole percent based on the terephthalate units, of a branching component containing at least three ester forming groups. The branching component can be one which provides branching in the acid unit portion of the polyester, or in the glycol unit portion, or it can be a hybrid. Illustrative of such branching components are tri- or tetracarboxylic acids, such as trimesic acid, pyromellitic acid, and lower alkyl esters thereof, and the like, or preferably, polyols, and especially preferably, tetrols, such as pentaerythritol; triols, such as trimethylol-propane; or dihydroxy carboxylic acids and hydroxydicarboxylic acids and derivatives, such as dimethyl hydroxyterephthalate, and the like.
The branched poly( 1 ,4-butylene terephthalate) resins and their preparation are described in
Borman, U.S. 3,953,404, incorporated herein by reference.
In certain preferred features the composition will include reinforcing fibrous (filamentous) glass.
The filamentous glass to be employed as reinforcement in such embodiments of the present compositions is well known to those skiiled in the art and is widely available from a number of manufacturers. For compositions ultimately to be employed for electrical uses, it is preferred to use fibrous glass filaments comprised of lime-aluminum borosilicate glass that is relatively soda free. This is known as "E" glass. However, other glasses are useful where electrical properties are not so important, e.g., the low soda glass known as "C" glass. The filaments are made by standard processes, e.g. by steam or air blowing, flame blowing and mechanical pulling. The preferred filaments for plastic reinforcement are made by mechanical pulling. The filament diameters range from about 0.00012 to 0.00075 inch, but this is not critical to the present invention.
The length of the glass filaments and whether or not they are bundled into fibers and the fibers bundled in turn to yarns, ropes or rovings, or woven into mats, and the like, are also not critical to the invention. However, in preparing the molding compositions, it is convenient to use the filamentous glass in the form of chopped strands of from about one-eighth to about 2 inches long. In articles molded from the compositions, on the other hand, even shorter lengths will be encountered because, during compounding, considerable fragmentation will occur. This is desirable, however, because the best properties are exhibited by thermoplastic injection molded articles in which the filament lengths lie between about 0.0005 and 0.250 inch.
The amount of the reinforcing glass can vary widely depending on the formulation and needs of the particular composition, it being essential only that an amount is selected which is at least sufficient to provide reinforcement. Preferably, however, the reinforcing fibrous glass will comprise from about 1 to about 60% by weight of fibrous glass and (a) and (b), combined.
It has also been discovered that the polyester compositions of this invention which contain modifiers and inorganic fillers e.g., talc, clays and the like, and fibrous glass exhibit improved impact and flexural properties when the glass is predispersed in the resin.
It has further been found that even relatively minor amounts of the modifier (b) are effective in
providing significant improvements in processability, etc. In general, however, the modifier (b) will be
present in amounts of at least about 1% by weight, preferably from about 2.5 to about 50% by weight
of (a) and (b). With amounts in excess of 50% by weight, some reduction in ease of processability may
be experienced.
Modifier (b) (i) a silane-treated clay can be made by treating finely divided reinforcing clay, e.g.,
kaolin clay, i.e., hydrophilic hydrous aluminum silicate, with a silane, e.g., vinyl tris-2-methoxy ethoxy
siiane to produce a silane-treated, readily dispersible clay. A preferred silane treated clay is made by
reacting kaolin with y-aminopropyl ethoxysilane, to produce an aminosilane-treated clay.
Modifier (b) (ii) acicular calcium metasiliate is known as wollastonite, and has become
commercially available as a filler for polyester, melamine, epoxy, urethane, nylon and vinyl resins. The
effectiveness can be enhanced by the use of silanes, as mentioned above for clay.
Modifier (b) (iii) comprises a combination of a segmented block copolyester, e.g., a block
polybutylene-co-poly-propylene glycol terephthalate resin in combination with an aromatic
polycarbonate, e.g., a bisphenol-A-phosgene resinous reaction product. These can be made in known
ways, and they are commercially available, e.g., the former as Hytrel 4055 from DuPont Company,
Wilmington, Del., U.S.A., and the latter as Lexan (@ from General Electric Co., Pittsfield, Mass., U.S.A.
The relative ratios of components in modifier (b) (iii) can vary broadly, e.g., from 1 to 99 parts of the
first to 99 to 1 parts of the second, but in general, from 60 to 40 parts of the segmented copolyester
will be present for each 40 to 60 parts of the aromatic polycarbonate per 1 00 parts by weight by (b)
(iii).
Novaculite is a well known commercial crystaliine microform of silica. Its use to fill polyesters is
described in Segal, U.S. 3,740,371, and in Rawlings U.S. 4,018,738, each of which is incorporated
herein by reference. A preferred commercially available form of novaculite is a treated type designated
Novakup 1 74-.05, by its supplier Malvern Minerals Co., of Hot Springs, Arkansas, U.S.A.
Other ingredients, such as dyes, pigments, flame retardants, drip retardants, and the like can be
added for their conventionally employed purposes.
The compositions of this invention can be prepared by a number of procedures. In one way, the
modifier and any reinforcement, e.g., glass fibers is put into an extrusion compounder with the resinous
components to produce molding pellets. The modifier, and reinforcement, if any, is dispersed in a
matrix of the resin in the process. In another procedure, the modifier is mixed with the resins by dry
blending, then either fluxed on a mill and comminuted, or they are extruded and chopped. The
modifying agent can also be mixed with the resins and directly molded, e.g., by injection or transfer
molding techniques.
It is always important to thoroughly free all of the ingredients; resin, modifier, reinforcement, if
used, and any optional, conventional additives from as much water as possible.
In addition, compounding should be carried out to ensure that the residence time in the machine
is short; the temperature is carefully controlled; the friction heat is utilized; and an intimate blend
between the resin and the modifier is obtained.
Although it is not essential, best results are obtained if the ingredients are pre-compounded,
pelletized and then molded. Pre-compounding can be carried out in conventional equipment. For
example, after carefully pre-drying the polyester and modifier and the reinforcing agent, if used, e.g., under vacuum at 1 000C for 12 hours, a single screw extruder is fed with a dry blend of the ingredients, the screw employed having a long transition section to ensure proper melting. On the other hand, a twin screw extrusion machine, e.g., a 28 mm Werner Pfleiderer machine can be fed with resin and additives at the feed port and reinforcement down stream. In either case, a generally suitable machine temperature will be about 450 to 4600 F.
The pre-compounded composition can be extruded and cut up into molding compounds such as conventional granules, pellets, etc., by standard techniques.
The composition can be molded in any equipment conventionally used for glass-filled thermoplastic compositions, e.g., a Newbury type injection molding machine with conventional cylinder temperatures, e.g., 450--5250F and conventional mold temperatures, e.g., 130-1 500F.
Description of the Preferred Embodiments
The following examples illustrate the invention. They are set forth as a further description but are not to be construed as limiting the invention thereto.
Examples 1 4 Dry blends of poly(1,4-butylene terephthalate) resin (PBT), intrinsic velocity 1.05 dl/g, melt viscosity 6,200 poise, poly(ethylene terephthalate) (PET), intrinsic velocity 0.62 dl/g, and silane-treated clay and mold release/stabilizer are compounded and extruded at 5200F in an extruder. The extrudate is pelletized and injection molded at 5200F (mold temperature 1 300F). The formulations and physical properties are shown in Table 1.
Table 1
Compositions Comprising Polyesters and
Silane-Treated Clay
Example lA* 1 2 3 4
Composition (parts by wt.) (parts Poly(1,4-butylene terephthalate) 60 54 48 42 36
Poly(ethylene terephthalate) 40 36 32 28 24
Silane-treated clay - 10 20 30 40
Properties
Warpage, room temperature, mm. < 1 < 1 < 1 < 1 < 1
Warpage after 30 min.at3500F.,mm. > 20 7 2 1 1
Unnotched Izod impact strength, ft.-lbs./in. 11.3 7.8 14.5 9.5 6.9
Notched Izod impact strength, ft.-lbs./ in. notch 0.5 0.4 0.4 0.3 0.3 *Control
Some difficulty in molding was found at 50 phr (parts per hundred resin) of silane-treated clay. In all of the examples the processability was excellent and the molded articles were very much improved in dimensional stability.
Examples 5-9
The general procedure of Examples 1-4 is employed to make compositions of poly(1 ,4-butylene terephthalate), poly(ethylene terephthalate) and acicular calcium metasilicate. The formulations used and the properties obtained are set forth in Table 2.
Table 2
Compositions Comprising Polyesters
and Acicular Calcium Metasilicate
Examples 5A* 5 6 7 8 9
Composition (parts by wt.J Poly(1,4-butylene terephthalate) 60 54 48 42 36 30
Poly(ethylene terephthalate) 40 36 32 28 24 20
Acicular calcium metasilicate - 10 20 30 40 50
Properties
Heat distort. temp.
at 264 psi. OF. 165 185 189 192 212 259
Warpage at R.T., mm. < 1 < 1 < 1 < 1 < 1 < 1
Warpage at 3500F., 30mien., mm. > 20 3 5 14 13 12
Notched Izod impact, ft-lbs/in. notch 0.5 0.5 0.5 0.6 0.7 0.7
Unnotched Izod impact, ft.-lbs./in. 11.3 4.0 5.9 7.3 6.9 4.9 *Control
All of the compositions of Examples 5-9 molded very easily in comparison to the control.
Examples 5 and 6, especially, were relatively warp-free and easy to process.
Examples 10-12
The general procedure of Examples 1-4 is used to make fibrous glass reinforced compositions
of poly(1,4-butyíene terephthalate), poly(ethylene terephthalate) and a modifier combination of a
segmented copolyester and an aromatic polycarbonate. The formulations used and the properties
obtained are set forth in Table 3::
Table 3
Reinforced Compositions Comprising Polyesters, Segmented
Copolyester and an Aromatic Polycarbonate
Example 10 11 12
Composition (parts by wtJ Poly(1,4-butylene terephthalate) 42.5 40 40
Poly(ethylene terephthalate) 30.0 30 30
Talc 15.0 15 15
Glass reinforcement 10.0 10 10
Blend-60 segmented copolyester and 40 aromatic polycarbonate 2.5 5 Blend-50 segmented copolyester and 50 aromatic polycarbonate - - 5
Properties
Heat distortion temp. 264 psi, OF. 361 - 358
Warp at R.T., mm. < 1 < 1 < 1
Warp after 30 min/3500F., mm 9 10 8
Notched Izod impact, ft. lbs./in. notch 1.0 1.0 0.9
Unnotched Izod impact ft.-lbs./in. 8.3 8.7 8.5
The compositions are very efficiently modified, especially in terms of impact strength, with the segmented copolyester-aromatic polycarbonate blends.
Examples 13-17 The general procedure of Examples 1-4 is used to make compositions of poly(1 ,4-butylene terephthalate), poly(ethylene terephthalate) and novaculite. The formulations used and the properties obtained are set forth in Table 4.
Tale 4 Compositions Comprising Polyesters and Novaculite
Example 13A* 13 14 15 16 17
Composition (parts by wt.) Poly(1,4-butylene terephthalate) 60 54 48 42 36 30
Poly(ethylene terephthalate) 40 36 32 28 24 20
Novaculite 0 10 20 30 40 50
Properties
Warpage at R.T., mm. < 1 < 1 < 1 < 1 < 1 < 1
Warpage after 30 min.
at3500F., mm > 20 15 5 4 < 1 < 1
Heat distortion temp.
at 264 psi, OF. 165 169 167 172 194
Unnotched Izod impact, ft.lbs./in. 11.3 11.1 8.2 N.B.** 15.5 12.2
Notched Izod impact, ft.lbs./in. notch 0.5 0.5 0.5 0.5 0.5 0.5 *Control **Did not break
All compositions of Examples 13-1 7 were easily molded. Especially at 30 and 40 parts of novaculite, low warpage and good unnotched Izod impact strength were seen.
Examples 18-25 The general procedure of Examples 1-4 is used to make compositions of poly(1,4-butylene terephthalate), aminosilane treated clay and a segmented copolyester. The formulations used and the properties obtained are set forth in Table 5.
Table 5
Compositions Comprising Polyester, Glass Fibers,
Aminosilane-treated Clay and Segmented Copolyester
Example 18 19 20 21 22 23 24 25
Composition(parts by wt.)
Poly(1,4-butylene terephthalate) 58 48 30 28 73 70 67 64 30% Fibrous glass-filled poly(1,4butylene terephthalate) 20 30 40 50 - - - @-aminipropylsilane-treated clay 14 14 14 14 14 14 14 14
Segmented copolyester 7 7 7 7 7 7 7 7
Fibrous glass - - - - 6 9 12 15
Properties
Heat distortion temp. at 264 psi, F 318 300 340 350 284 348 354 363
Warp at R.T., mm. < 1 < 1 < 1 < 1 1 6 6 13
Warp at 30 min. 350 F., mm. 4 6 12 19 8 14 17 18
Notched Izod impact, ft.lbs./in. notch 1.3 1.4 1.4 1.7 1.2 1.3 1.3 1.2
Unnotched Izod impact, ft.lbs./in. 13.8 12.2 12.1 11.4 12.3 9.6 9.3 9.1
Flexural str., psi 14,700 16,700 17,500 19,000 13,500 15,500 16,700 17,500
Flexural mod., psi 491,000 709,000 604,000 716,000 The compositions have low warp after molding and expecially excellent impact strength. It can also be noted that precompounding the glass fibers into the polyester resin prior to blending (Examples 18-21) with the remaining ingredients leads to lower warpage and improved impact and flexural strengths.
Obviously, other modifications and variations of the present invention are possible in the light of the above teachings. It is therefore, to be understood that changes may be made in the particular embodiments described above which are within the scope of the invention as defined in the appended
Claims (11)
1. A thermoplastic composition which comprises
(a) a polyester composition comprising a poly{1 ,4-butylene terephthalate) resin or an intimate mixture of a poly(1,4-butylene terephthalate) resin and a poly(ethylene terephthalate) resin; and
(b) up to 60 parts per 100 parts by weight of (a) and (b) of a modifier therefor comprising:
(i) a silane-treated clay;
(ii) acicular calcium metasilicate
(iii) a combination of a segmented copolyester and an aromatic polycarbonate; or
(iv) novaculite, or a mixture thereof.
2. A composition as claimed in Claim 1 wherein the modifier (b) is present in an amount of at least 1.0% by weight of (a) and (b).
3. A composition as claimed in Claim 2 wherein the amount of modifier (b) is from 2.5 to 50% by weight of (a) and (b).
4. A composition as claimed in any preceding Claim which also includes from 1 to 60% by weight of reinforcing fibrous glass based on (a), (b) and said fibrous glass.
5. A thermoplastic composition as claimed in Claim 4 wherein said fibrous glass is pre-dispersed in component (a).
6. A composition as claimed in any preceding Claim wherein said polyester resin (a) has an intrinsic velocity of at least 0.4 deciliters/gram when measured in a solution in a 60:40 mixture of phenol and trichloroethane at 300 C.
7. A composition as claimed in Claim 6 wherein said intrinsic viscosity is at least 0.6 deciliters per gram.
8. A composition as claimed in any preceding Claim wherein said poly(1 ,4-butylene terephthalate) resin is linear or branched.
9. A composition as claimed in Claim 8 wherein said branched polyester is a high melt viscosity (1,4-butylene terephthalate) resin which includes a small amount of a branching component containing at least three ester forming groups.
10. A composition as claimed in any preceding claim wherein said modifier (b) is an aminosilanetreated clay.
11. A composition as claimed in Claim 1 and substantially as hereinbefore described with reference to any of Examples 1 to 25.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB7914500A GB2048285B (en) | 1979-04-26 | 1979-04-26 | Polyester compositions |
GB08308605A GB2123014B (en) | 1979-04-26 | 1983-03-29 | Modified polyester compositions |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB7914500A GB2048285B (en) | 1979-04-26 | 1979-04-26 | Polyester compositions |
Publications (2)
Publication Number | Publication Date |
---|---|
GB2048285A true GB2048285A (en) | 1980-12-10 |
GB2048285B GB2048285B (en) | 1983-10-19 |
Family
ID=10504785
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB7914500A Expired GB2048285B (en) | 1979-04-26 | 1979-04-26 | Polyester compositions |
Country Status (1)
Country | Link |
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GB (1) | GB2048285B (en) |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2250024A (en) * | 1990-11-13 | 1992-05-27 | T & N Technology Ltd | Gaskets |
WO1993004118A1 (en) * | 1991-08-12 | 1993-03-04 | Allied-Signal Inc. | Melt process formation of polymer nanocomposite of exfoliated layered material |
EP0899308A1 (en) * | 1996-05-13 | 1999-03-03 | Kaneka Corporation | Thermoplastic resin composition containing clay composite and process for preparing the same |
EP1026203A1 (en) * | 1997-10-30 | 2000-08-09 | Kaneka Corporation | Polyester resin compositions and processes for the preparation thereof |
US7799838B2 (en) | 2006-07-26 | 2010-09-21 | Sabic Innovative Plastics Ip B.V. | Elastomer blends of polyesters and copolyetheresters derived from polyethylene terephthalate, method of manufacture, and articles therefrom |
US7807745B2 (en) | 2006-01-27 | 2010-10-05 | Sabic Innovative Plastics Ip B.V. | Molding compositions containing polycarbonate and modified polybutylene terephthalate (PBT) random copolymers derived from polyethylene terephthalate (PET) |
US7855238B2 (en) | 2006-01-27 | 2010-12-21 | Sabic Innovative Plastics Ip B.V. | Molding compositions containing polyalkylene terephthalates and modified polybutylene terephthalate (PBT) random copolymers derived from PET |
US7902263B2 (en) | 2006-01-27 | 2011-03-08 | Sabic Innovative Plastics Ip B.V. | Process for making polybutylene terephthalate (PBT) from polyethylene terephthalate (PET) |
US7935737B2 (en) | 2006-01-27 | 2011-05-03 | Sabic Innovative Plastics Ip B.V. | Articles derived from compositions containing modified polybutylene terephthalate (PBT) random copolymers derived from polyethylene terephthalate (PET) |
US8067493B2 (en) | 2003-12-30 | 2011-11-29 | Sabic Innovative Plastics Ip B.V. | Polymer compositions, method of manufacture, and articles formed therefrom |
US8129471B2 (en) | 2009-12-30 | 2012-03-06 | Sabic Innovative Plastics Ip B.V. | Polycarbonate-poly(ether-ester) copolymer composition, method of manufacture, and articles therefrom |
US8158710B2 (en) | 2006-11-27 | 2012-04-17 | Sabic Innovative Plastics Ip B.V. | Polyester blends, methods of making, and articles formed therefrom |
US8309656B2 (en) | 2006-07-26 | 2012-11-13 | Sabic Innovative Plastics Ip B.V. | Elastomer blends containing polycarbonates and copolyetheresters derived from polyethylene terephthalate, method of manufacture, and articles therefrom |
-
1979
- 1979-04-26 GB GB7914500A patent/GB2048285B/en not_active Expired
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2250024A (en) * | 1990-11-13 | 1992-05-27 | T & N Technology Ltd | Gaskets |
WO1993004118A1 (en) * | 1991-08-12 | 1993-03-04 | Allied-Signal Inc. | Melt process formation of polymer nanocomposite of exfoliated layered material |
EP0899308A1 (en) * | 1996-05-13 | 1999-03-03 | Kaneka Corporation | Thermoplastic resin composition containing clay composite and process for preparing the same |
EP0899308A4 (en) * | 1996-05-13 | 1999-03-03 | ||
US6239195B1 (en) | 1996-05-13 | 2001-05-29 | Kaneka Corporation | Thermoplastic resin composition containing silan-treated foliated phyllosilicate and method for producing the same |
EP1026203A1 (en) * | 1997-10-30 | 2000-08-09 | Kaneka Corporation | Polyester resin compositions and processes for the preparation thereof |
EP1026203A4 (en) * | 1997-10-30 | 2003-01-02 | Kaneka Corp | Polyester resin compositions and processes for the preparation thereof |
US6583208B1 (en) | 1997-10-30 | 2003-06-24 | Kaneka Corporation | Polyester resin compositions and processes for the preparation thereof |
US8067493B2 (en) | 2003-12-30 | 2011-11-29 | Sabic Innovative Plastics Ip B.V. | Polymer compositions, method of manufacture, and articles formed therefrom |
US7935737B2 (en) | 2006-01-27 | 2011-05-03 | Sabic Innovative Plastics Ip B.V. | Articles derived from compositions containing modified polybutylene terephthalate (PBT) random copolymers derived from polyethylene terephthalate (PET) |
US7855238B2 (en) | 2006-01-27 | 2010-12-21 | Sabic Innovative Plastics Ip B.V. | Molding compositions containing polyalkylene terephthalates and modified polybutylene terephthalate (PBT) random copolymers derived from PET |
US7902263B2 (en) | 2006-01-27 | 2011-03-08 | Sabic Innovative Plastics Ip B.V. | Process for making polybutylene terephthalate (PBT) from polyethylene terephthalate (PET) |
US7807745B2 (en) | 2006-01-27 | 2010-10-05 | Sabic Innovative Plastics Ip B.V. | Molding compositions containing polycarbonate and modified polybutylene terephthalate (PBT) random copolymers derived from polyethylene terephthalate (PET) |
US8138233B2 (en) | 2006-01-27 | 2012-03-20 | Sabic Innovative Plastics Ip B.V. | Process for making polybutylene terephthalate (PBT) from polyethylene terephthalate (PET) |
US7799838B2 (en) | 2006-07-26 | 2010-09-21 | Sabic Innovative Plastics Ip B.V. | Elastomer blends of polyesters and copolyetheresters derived from polyethylene terephthalate, method of manufacture, and articles therefrom |
US8309656B2 (en) | 2006-07-26 | 2012-11-13 | Sabic Innovative Plastics Ip B.V. | Elastomer blends containing polycarbonates and copolyetheresters derived from polyethylene terephthalate, method of manufacture, and articles therefrom |
US8735505B2 (en) | 2006-07-26 | 2014-05-27 | Sabic Innovative Plastics Ip B.V. | Elastomer blends containing polycarbonates and copolyetheresters derived from polyethylene terephthalate, method of manufacture, and articles therefrom |
US8158710B2 (en) | 2006-11-27 | 2012-04-17 | Sabic Innovative Plastics Ip B.V. | Polyester blends, methods of making, and articles formed therefrom |
US8129471B2 (en) | 2009-12-30 | 2012-03-06 | Sabic Innovative Plastics Ip B.V. | Polycarbonate-poly(ether-ester) copolymer composition, method of manufacture, and articles therefrom |
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GB2048285B (en) | 1983-10-19 |
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PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19960426 |