CA1176390A - High impact resistant composition including polyethylene terephthalates and abs grafted polymer - Google Patents
High impact resistant composition including polyethylene terephthalates and abs grafted polymerInfo
- Publication number
- CA1176390A CA1176390A CA000394001A CA394001A CA1176390A CA 1176390 A CA1176390 A CA 1176390A CA 000394001 A CA000394001 A CA 000394001A CA 394001 A CA394001 A CA 394001A CA 1176390 A CA1176390 A CA 1176390A
- Authority
- CA
- Canada
- Prior art keywords
- weight
- polymer
- composition according
- graft
- reinforcing material
- 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.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
Abstract
ABSTRACT
High impact resistant polyalkylene terephthalates The toughness of polyalkylene terephthalates may be substantially increased by adding an ABS graft polymer having a relatively high content of graft base and a narrowly-defined particle size, without the typical characteristics of the polyalkylene terephthalates, such as high dimensional stability to heat, hardness and rigidity being too greatly influenced. The products have an excellent multi-axial impact resistance.
Le A 20 848
High impact resistant polyalkylene terephthalates The toughness of polyalkylene terephthalates may be substantially increased by adding an ABS graft polymer having a relatively high content of graft base and a narrowly-defined particle size, without the typical characteristics of the polyalkylene terephthalates, such as high dimensional stability to heat, hardness and rigidity being too greatly influenced. The products have an excellent multi-axial impact resistance.
Le A 20 848
Description
HIGH IMPACT RESISTANT POLYALKYLENE T~REPHTHALATES
This invention relates to high impact resistant mixtures of polyalkylene terephthalates and ABS graft polymers having a specific composition and a narrowly-defined particle size.
Polyalkylene terephthalates have become very important in the field of thermoplastic moulding compositions, due to the val-uable technological characteristics thereof, for example rigidity, hardness, abrasion resistance, dynamic and thermal stressing capacity and rapid processibility. A disadvantage of these mould-ing compositions is the occas~onally inadequate multi-axial (two dimensional) ~mpact strength thereof.
There are numerous proposals for increasing the toughness of thermoplastic polyesters by admixing or condensing therein other polymers, in particular those based on modified elastomers and polyolefins (German Offenlegungsschrift Nos. 1,694,173;
1,928,369; 2,248,242; 2,310,034; 2,357,406; and 2,364,318; German Auslegeschrift Nos. 1,961,226 and 1,962,855 and United States Patent Nos. 3,236,914 and 3,723,574). ~owever, the proposed measures have the disadvantage that an improve~ent in toughness is accompanied by a substantial deteriorat-~on in other characteristics, for example in the above-mentioned characteristics. Moreover, the desired multi-axial impact strength is not achieved.
Surpris~ngly, it has now been found that -the above dis-advantages may be overcome if certa~n ABS graft polymers, mainly those which have a relatively high content of graft base and a narrowly-defined particle size, are selected.
The present invention provides a polymer composition consisting of (~) from 65 to 99%, by weight, of polyalkylene terephthalate which consists of (a) from 1 to 100~ by weight of polyethylene terephthalate; and (b) from 99 to 0% by weight of polybutylene terephthalate; and (B) from 1 to 35% by weight o~ ABS
graft polymer, the percentages of (~) and (B) being based on the sum of (A) + (s) and the percentages of (a) and (b) being based on (A), the graft polymer (B) being obtained by a grafting reaction of tI) fn~llO to`40% by weight based on (B) of a mixture consisting of:
(a) from 10 to 35% by weight based on the total of (a) + (b), of acrylonitrile, and (b) from 65 to 90% by weight based on the sum of (a) + (b), of styrene; on (II) from 60 to 90% by weight based on (B) of a crosslinked butadiene polymer containing at least 70% by weight based on (II) of butadiene radicals as the graft base;
wherein the gel content of the graft base (II) is at least 70%
(measured in toluene), the grafting degree of the graft polymer (G) is from 0.15 to 0.55 and the average particle diameter d50 of the ABS graft polymer (B) is from 0.2 to 0.6 ~m.
The present invention also provides a moulding composition which comprises the polymer composition mentioned above and a re-inforcing glass fibre, wherein the amount of the glass fibre in the moulding composit~on ;~s 5 to 50% by weight.
The above-mentioned polymer composition preferably consists of from 70 to 98%, more preferably from 75 to 97% by weight of the polyalkylene terephthalate and 2 to 30%, more preferably from 3 to 25% of the ABS graft polymer.
The polyalkylene terephthalate comprises preferably (al from 10 to 80%, more preferably form 30 to 60~ by weight of poly-ethylene terephthalate; and (b) from 90 to 20%, more preferably from 70 to 40% by weight of polybutylene terephthalate.
This invention relates to high impact resistant mixtures of polyalkylene terephthalates and ABS graft polymers having a specific composition and a narrowly-defined particle size.
Polyalkylene terephthalates have become very important in the field of thermoplastic moulding compositions, due to the val-uable technological characteristics thereof, for example rigidity, hardness, abrasion resistance, dynamic and thermal stressing capacity and rapid processibility. A disadvantage of these mould-ing compositions is the occas~onally inadequate multi-axial (two dimensional) ~mpact strength thereof.
There are numerous proposals for increasing the toughness of thermoplastic polyesters by admixing or condensing therein other polymers, in particular those based on modified elastomers and polyolefins (German Offenlegungsschrift Nos. 1,694,173;
1,928,369; 2,248,242; 2,310,034; 2,357,406; and 2,364,318; German Auslegeschrift Nos. 1,961,226 and 1,962,855 and United States Patent Nos. 3,236,914 and 3,723,574). ~owever, the proposed measures have the disadvantage that an improve~ent in toughness is accompanied by a substantial deteriorat-~on in other characteristics, for example in the above-mentioned characteristics. Moreover, the desired multi-axial impact strength is not achieved.
Surpris~ngly, it has now been found that -the above dis-advantages may be overcome if certa~n ABS graft polymers, mainly those which have a relatively high content of graft base and a narrowly-defined particle size, are selected.
The present invention provides a polymer composition consisting of (~) from 65 to 99%, by weight, of polyalkylene terephthalate which consists of (a) from 1 to 100~ by weight of polyethylene terephthalate; and (b) from 99 to 0% by weight of polybutylene terephthalate; and (B) from 1 to 35% by weight o~ ABS
graft polymer, the percentages of (~) and (B) being based on the sum of (A) + (s) and the percentages of (a) and (b) being based on (A), the graft polymer (B) being obtained by a grafting reaction of tI) fn~llO to`40% by weight based on (B) of a mixture consisting of:
(a) from 10 to 35% by weight based on the total of (a) + (b), of acrylonitrile, and (b) from 65 to 90% by weight based on the sum of (a) + (b), of styrene; on (II) from 60 to 90% by weight based on (B) of a crosslinked butadiene polymer containing at least 70% by weight based on (II) of butadiene radicals as the graft base;
wherein the gel content of the graft base (II) is at least 70%
(measured in toluene), the grafting degree of the graft polymer (G) is from 0.15 to 0.55 and the average particle diameter d50 of the ABS graft polymer (B) is from 0.2 to 0.6 ~m.
The present invention also provides a moulding composition which comprises the polymer composition mentioned above and a re-inforcing glass fibre, wherein the amount of the glass fibre in the moulding composit~on ;~s 5 to 50% by weight.
The above-mentioned polymer composition preferably consists of from 70 to 98%, more preferably from 75 to 97% by weight of the polyalkylene terephthalate and 2 to 30%, more preferably from 3 to 25% of the ABS graft polymer.
The polyalkylene terephthalate comprises preferably (al from 10 to 80%, more preferably form 30 to 60~ by weight of poly-ethylene terephthalate; and (b) from 90 to 20%, more preferably from 70 to 40% by weight of polybutylene terephthalate.
- 2 -....
The graft polymer (B) is obtained by a grafting reaction of: preferably (I) from 10 to 35%, more preferably from 15 to 25%, by weight, based on (B), of a mixture comprising: (a) from 10 to 35%, preferably from 20 to 35%, by weight of acrylonitrile, based on the sum of (a) + (b); and (b) from 65 to 90%, preferably from 65 to 80~, by weight, of styrene, based on the sum of (a) + (b);
on (II) from 65 to 90%, more preferably from 75 to 85% by weight based on (B) of a crosslinked butadiene polymer containing at least 70%, by weight based on (II), of butadiene radicals as the graft base.
The gel content of the ~raft base (II~ preferably at least 80% (measured in toluene), the average particle diameter d50 of the ABS graft polymer (B) is preferably from 0.3 to 0.5 ~m, more pre-ferably about 0.4 ~m.
The polyalkylene terephthalates (A) contain at least 90 mol %, based on the dicarboxylic acid component, of terephthalic acid radicals and at least 90 mol %, based on the diol component, of ethylene glycol radicals or a mixture of ethylene glycol radicals and butane-1,4-diol radicals.
In this specification, the polymer composition may be simply referred to as "mixture"~
In addition to containing terephthalic acid groups, the polyalkylene terephthalates~ (~) may also contain up to 10 mol ~ of residues of other aromatic, aliphatic or cycloaliphatIc dicarboxy-lic ac~ds, for example succinic acid, adipic acid and isophthalic acid, In add~tion to containing ethylene glycol groups or a mix-ture thereof with ~utane diol groups, they may also contain up to 10 mol % of residues of another diol, which diol may correspond to .~
~ - 3 -~63~
the following general formula:
wherein n represents an integer of from 2 to 10. In particular, there may also be incorporated up to 10 mol % of alkyl-substituted diols, such as neopentyl glycol, 2,2,4-trimethylhexane diol-1,6, 2-ethyl-propane diol-1,3,2,2,4-trimethyl pentane diol-1,3, 2-methyl-pentane diol-2,4, 3-methyl pentane diol-2,4 and 2-ethyl hexane diol-1,3, (Germany Offenlegungsschrift Nos. 2,407,674; 2,407,776 and 2,715,932).
The polyalkylene terephthalates (A) may also be hranched by branching compounds, such as polycarboxylic acids or polyols (German Auslegeschr~ft No. 1,900,270).
The polyethylene terephthalates used as component (A) generally have an ~ntrInsIc viscos~ty of from 0.5 to 1.5 dl/g, preferably from 0.6 to 1.3 dl/g, more preferably from 0.7 to 1.2 dl/g and the polybutylene terephthalates used as component (A) gen-erally have an ~ntrins~c viscosIty of from 0~7 to 1.5 dl/g, preferably from 0.8 to lo 3 dl~g, more preferably from 0~ to 1.05 dl/g, in each case measured ~n phenol/o-dichlorobenzene at 25C
(1:1 parts, by weight).
In add~tion to containing butadiene radicals, the graft base (II) may also conta~n up to 30%, by weight, based on (II), of rad;~cals of other ~,~ ~ethylenically unsaturated monomers, for example styrene, acrylonitrile, esters of acrylic or methacrylic acids containing from 1 to 4 carbon atoms in the alcohol component (such as metacrylate, ethyl acrylate, methyl. methacrylate and ethyl methacrylate), The preferred graft base ~II) is pure polybutadiene.
Since it is known that, during gra~ting, the graft ...~, ~ 4 -39~
monomers (I) do not completely graft onto the yraft base (II), in the present context the term "graft polymers" is to be unders-tood to include those products which contain homo- and co-polymers of the graft monomers (I) used, in addition to the actual graft polymers. The degree of grafting G characterises the ratio of styrene/acrylonitrile copolymer: graft base and it is non-dimensional.
The average particle diameter d50 is the diameter above and below which lie repsectively 50%, by weight, of the particles.
The average particle diameter may be determined by ultra-centrifugal measurements (~. Scholtan, H. Lange, Kolloid. Z. and Z. Polymere 250 (1972), 782-796) or by electron microscopy and by subsequently counting the particles (G. Kampf, H. Schuster, Angew.
Makromolekulare Chemie 14 (1970), 111 - 129).
The graft polymers (B) may be prepared by known methods for example by emuls~on polymerisr~tion or latex~suspension processes, using radical-forming polymerisation ;nitiators in a polybutadiene or butadiene copolymer latex.
Processes for the productIon of AsS graft polymers are known.
The polymer composition according to the present invention may be produced using con~entional mixing apparatus, such as rollers, kneaders and single- and multi-screw extruders. Twin-screw extrud-ers and kneaders are particularly suitable.
The mixtures may be produced using the abo~e mixing apparatus eIther by melting the two components (~) and (B) together and homogenising or by mixIng the graft polymer (B) into the melt of the polyalkylene terephthalate (A).
` ? - 5 The temperature during the production of the mixtures should be at least 10C above the melting point of the polyalkylene terephthalate (A) and should be below 300C, preferably from 2~5 to 280C. The lower temperature should be for the mixtures with high PBT-content, the higher temperature for those with high PET-content.
The polymer composition according to the present invention as such may be used as a moulding compound, however it may be ad-mixed with conventional additives, such as lubricants and mould-release agents, nucleation agents, stabilisers, fillers and rein-forcing materials, flameproofing agents and dyes. Such materials are preferably added during the compounding operation, in a pure form or as a concentrate.
The moulding compound according to the present invention may contain from 5 to 60~, preferably from 5 to 50~, more prefer-ably from 10 to 40% by weight based on the sum of the polymer composition and the reinforcing material of a reinforcing material.
Glass fibres are preferred reinforcing materials. Preferred fillers which may also have a re~nforcing effect are glass beads, mica, silicates, quartz, talcum, titanium dioxide and wollastonite.
Those moulding compounds provided with flameproofing agents generally contain such flameproofing agents in an a~ount of less than 30%, by weight, based on the mould~ng compound.
Various known flameproofing agents are included, for ex-ample, polyhalogen diphenyl, polyhalogen diphenyl ether, polyhalogen phthalic acid and derIvatives thereof and polyhalogen polycarbon-ates, the bromine compounds being particularly effective. P~oreover, the moulding compounds usually contain a synergist, for example, -~ - 6 -~ ~17~
antimony trioxide.
The polymer compositions and the moulding compounds accord-ing to the present invention are distinguished by low contents of graft polymer (B), by a considerable improvement in the multi-axial impact resistance, in particular at temperatures as low as -40C.
It is also surprising that the polymer compositions and the mould-ing compounds have a high weld line strength, and they are also distinguished by a high dimensional stability to heat.
Therefore, in accordance with the property spectrum, the polymer compositions according to the present invention may be widely used in the injection moulding and extrusion sector, where a high dimensional stability to heat and a high strength, in con-junction with a high solvent resistance, are required, for example, in the case of thermally stressed household gadgets, car body parts, bumpers, component parts for office machines and lamp holders.
Figure 1 is a vert~cal cross sectional view of a test box prepared from a moulding compound for testing the properties thereof;
Figure 2 is a txansverse cross section of the box of Figure l; and Figure 3 is a perspectIve view of the box of Figure 1 and a rod for providing a test ball.
Details of the Figures are described w~th respect to Examples 14 to 19.
The parts specified in the following Examples are parts, by weight.
Examples 1 to 13 ;~ - 7 ~ polyethylene terephthalate having an intrinsic viscosity of 0.75 dl/g alone or in an admixture with a polybut~lene tere-phthalate having an intrinsic viscosity of 0.95 dl/g was melted down on continuously operating twin-screw extruder produced by Werner & Pfleiderer (type ZSK 32). The ABS graft polymer was in-troduced inot the polyalkylene terephthalate melt through a second inlet pipe. Blanketing with nitrogen is appropriate. The graft polymer was melted and was homogeneously distributed in the poly-alkylene terephthalate. It may be advantageous to degas the melt before it issues from the die, The cylinder temperatures were ad-justed such that a mass temperature of from 265 to 270C was ensured. The molten strand of the mixture of polyalkylene tere-phthalate and graft polymer was cooled in water, granulated and dried.
For the preparation of the graft polymer, quantities spec-ified in Table 1 of acrylonitrile and styrene were grafted onto from 65 to 80 parts of a coarsely-particulate, cross-linked poly-butad~ene rubber having an average particle diameter of the poly-butadiene graft base present in latex form of 0.4 Jum and a gel content of 85%, by emulsion polymerisation in accordance with German Auslegeschrift Nos. 1,247,665 and 1,269,360.
Standard small test bars (according to DIN 53 453) and plates having dImensions of 3 x 60 x 60 mm were extruded from the granulated materlal using a conventlonal injection moulding machine at a mass temperature of from 265 to 270C.
The following p~operties were tested: the impact strength and notched impact strength (accord;~ng to DIN 53 453), the indentation hardness (according to DIN 53 456), the dimensional - 7a -stability to heat according to Vicat (in accordance with DIN
53 460) and the multi-~ ~ 7b -axial impact strength in the EKWA test (DIN 53 443), sheet 2, penetration of a plate having dimensions of
The graft polymer (B) is obtained by a grafting reaction of: preferably (I) from 10 to 35%, more preferably from 15 to 25%, by weight, based on (B), of a mixture comprising: (a) from 10 to 35%, preferably from 20 to 35%, by weight of acrylonitrile, based on the sum of (a) + (b); and (b) from 65 to 90%, preferably from 65 to 80~, by weight, of styrene, based on the sum of (a) + (b);
on (II) from 65 to 90%, more preferably from 75 to 85% by weight based on (B) of a crosslinked butadiene polymer containing at least 70%, by weight based on (II), of butadiene radicals as the graft base.
The gel content of the ~raft base (II~ preferably at least 80% (measured in toluene), the average particle diameter d50 of the ABS graft polymer (B) is preferably from 0.3 to 0.5 ~m, more pre-ferably about 0.4 ~m.
The polyalkylene terephthalates (A) contain at least 90 mol %, based on the dicarboxylic acid component, of terephthalic acid radicals and at least 90 mol %, based on the diol component, of ethylene glycol radicals or a mixture of ethylene glycol radicals and butane-1,4-diol radicals.
In this specification, the polymer composition may be simply referred to as "mixture"~
In addition to containing terephthalic acid groups, the polyalkylene terephthalates~ (~) may also contain up to 10 mol ~ of residues of other aromatic, aliphatic or cycloaliphatIc dicarboxy-lic ac~ds, for example succinic acid, adipic acid and isophthalic acid, In add~tion to containing ethylene glycol groups or a mix-ture thereof with ~utane diol groups, they may also contain up to 10 mol % of residues of another diol, which diol may correspond to .~
~ - 3 -~63~
the following general formula:
wherein n represents an integer of from 2 to 10. In particular, there may also be incorporated up to 10 mol % of alkyl-substituted diols, such as neopentyl glycol, 2,2,4-trimethylhexane diol-1,6, 2-ethyl-propane diol-1,3,2,2,4-trimethyl pentane diol-1,3, 2-methyl-pentane diol-2,4, 3-methyl pentane diol-2,4 and 2-ethyl hexane diol-1,3, (Germany Offenlegungsschrift Nos. 2,407,674; 2,407,776 and 2,715,932).
The polyalkylene terephthalates (A) may also be hranched by branching compounds, such as polycarboxylic acids or polyols (German Auslegeschr~ft No. 1,900,270).
The polyethylene terephthalates used as component (A) generally have an ~ntrInsIc viscos~ty of from 0.5 to 1.5 dl/g, preferably from 0.6 to 1.3 dl/g, more preferably from 0.7 to 1.2 dl/g and the polybutylene terephthalates used as component (A) gen-erally have an ~ntrins~c viscosIty of from 0~7 to 1.5 dl/g, preferably from 0.8 to lo 3 dl~g, more preferably from 0~ to 1.05 dl/g, in each case measured ~n phenol/o-dichlorobenzene at 25C
(1:1 parts, by weight).
In add~tion to containing butadiene radicals, the graft base (II) may also conta~n up to 30%, by weight, based on (II), of rad;~cals of other ~,~ ~ethylenically unsaturated monomers, for example styrene, acrylonitrile, esters of acrylic or methacrylic acids containing from 1 to 4 carbon atoms in the alcohol component (such as metacrylate, ethyl acrylate, methyl. methacrylate and ethyl methacrylate), The preferred graft base ~II) is pure polybutadiene.
Since it is known that, during gra~ting, the graft ...~, ~ 4 -39~
monomers (I) do not completely graft onto the yraft base (II), in the present context the term "graft polymers" is to be unders-tood to include those products which contain homo- and co-polymers of the graft monomers (I) used, in addition to the actual graft polymers. The degree of grafting G characterises the ratio of styrene/acrylonitrile copolymer: graft base and it is non-dimensional.
The average particle diameter d50 is the diameter above and below which lie repsectively 50%, by weight, of the particles.
The average particle diameter may be determined by ultra-centrifugal measurements (~. Scholtan, H. Lange, Kolloid. Z. and Z. Polymere 250 (1972), 782-796) or by electron microscopy and by subsequently counting the particles (G. Kampf, H. Schuster, Angew.
Makromolekulare Chemie 14 (1970), 111 - 129).
The graft polymers (B) may be prepared by known methods for example by emuls~on polymerisr~tion or latex~suspension processes, using radical-forming polymerisation ;nitiators in a polybutadiene or butadiene copolymer latex.
Processes for the productIon of AsS graft polymers are known.
The polymer composition according to the present invention may be produced using con~entional mixing apparatus, such as rollers, kneaders and single- and multi-screw extruders. Twin-screw extrud-ers and kneaders are particularly suitable.
The mixtures may be produced using the abo~e mixing apparatus eIther by melting the two components (~) and (B) together and homogenising or by mixIng the graft polymer (B) into the melt of the polyalkylene terephthalate (A).
` ? - 5 The temperature during the production of the mixtures should be at least 10C above the melting point of the polyalkylene terephthalate (A) and should be below 300C, preferably from 2~5 to 280C. The lower temperature should be for the mixtures with high PBT-content, the higher temperature for those with high PET-content.
The polymer composition according to the present invention as such may be used as a moulding compound, however it may be ad-mixed with conventional additives, such as lubricants and mould-release agents, nucleation agents, stabilisers, fillers and rein-forcing materials, flameproofing agents and dyes. Such materials are preferably added during the compounding operation, in a pure form or as a concentrate.
The moulding compound according to the present invention may contain from 5 to 60~, preferably from 5 to 50~, more prefer-ably from 10 to 40% by weight based on the sum of the polymer composition and the reinforcing material of a reinforcing material.
Glass fibres are preferred reinforcing materials. Preferred fillers which may also have a re~nforcing effect are glass beads, mica, silicates, quartz, talcum, titanium dioxide and wollastonite.
Those moulding compounds provided with flameproofing agents generally contain such flameproofing agents in an a~ount of less than 30%, by weight, based on the mould~ng compound.
Various known flameproofing agents are included, for ex-ample, polyhalogen diphenyl, polyhalogen diphenyl ether, polyhalogen phthalic acid and derIvatives thereof and polyhalogen polycarbon-ates, the bromine compounds being particularly effective. P~oreover, the moulding compounds usually contain a synergist, for example, -~ - 6 -~ ~17~
antimony trioxide.
The polymer compositions and the moulding compounds accord-ing to the present invention are distinguished by low contents of graft polymer (B), by a considerable improvement in the multi-axial impact resistance, in particular at temperatures as low as -40C.
It is also surprising that the polymer compositions and the mould-ing compounds have a high weld line strength, and they are also distinguished by a high dimensional stability to heat.
Therefore, in accordance with the property spectrum, the polymer compositions according to the present invention may be widely used in the injection moulding and extrusion sector, where a high dimensional stability to heat and a high strength, in con-junction with a high solvent resistance, are required, for example, in the case of thermally stressed household gadgets, car body parts, bumpers, component parts for office machines and lamp holders.
Figure 1 is a vert~cal cross sectional view of a test box prepared from a moulding compound for testing the properties thereof;
Figure 2 is a txansverse cross section of the box of Figure l; and Figure 3 is a perspectIve view of the box of Figure 1 and a rod for providing a test ball.
Details of the Figures are described w~th respect to Examples 14 to 19.
The parts specified in the following Examples are parts, by weight.
Examples 1 to 13 ;~ - 7 ~ polyethylene terephthalate having an intrinsic viscosity of 0.75 dl/g alone or in an admixture with a polybut~lene tere-phthalate having an intrinsic viscosity of 0.95 dl/g was melted down on continuously operating twin-screw extruder produced by Werner & Pfleiderer (type ZSK 32). The ABS graft polymer was in-troduced inot the polyalkylene terephthalate melt through a second inlet pipe. Blanketing with nitrogen is appropriate. The graft polymer was melted and was homogeneously distributed in the poly-alkylene terephthalate. It may be advantageous to degas the melt before it issues from the die, The cylinder temperatures were ad-justed such that a mass temperature of from 265 to 270C was ensured. The molten strand of the mixture of polyalkylene tere-phthalate and graft polymer was cooled in water, granulated and dried.
For the preparation of the graft polymer, quantities spec-ified in Table 1 of acrylonitrile and styrene were grafted onto from 65 to 80 parts of a coarsely-particulate, cross-linked poly-butad~ene rubber having an average particle diameter of the poly-butadiene graft base present in latex form of 0.4 Jum and a gel content of 85%, by emulsion polymerisation in accordance with German Auslegeschrift Nos. 1,247,665 and 1,269,360.
Standard small test bars (according to DIN 53 453) and plates having dImensions of 3 x 60 x 60 mm were extruded from the granulated materlal using a conventlonal injection moulding machine at a mass temperature of from 265 to 270C.
The following p~operties were tested: the impact strength and notched impact strength (accord;~ng to DIN 53 453), the indentation hardness (according to DIN 53 456), the dimensional - 7a -stability to heat according to Vicat (in accordance with DIN
53 460) and the multi-~ ~ 7b -axial impact strength in the EKWA test (DIN 53 443), sheet 2, penetration of a plate having dimensions of
3 x 60 x 60 mm and by a 35 kg weight with spherical tipped penetra~ion spike, diameter 20 mm, falling from a height of 1 m).
The weld line strength was tested (in the tensile strength test according to DIN 53 455) using tensile test bars injection-moulded at both ends.
Le A 20 848 3~
g ~3 ~3 (D
_ tD
_~ ~ H
H (D
H It --~ G~
. ~ pJ
~t ~h r~
~¢ (D ~
P~ O
co CO ~ ~h O ~_ O O U~ ~h ~
(D
O O
~ ^W
W ~
--(D
(D
~Q tD
Q
l_ ,_ ~ ~ O
c ~o ~ r~
J.
~-I~
O~ ~
~ ~h CO ~I ~I
CC~ N ~ It m ,_ -GS
Hl ~' o o o ~
I_ O ~n tD
tD
G~
Le A 20 848 W ~ O ~ , x 0~ j I 1- H
_ I 11 4 o !~ ~o~
o~
~ 3 , ~
ll I l ll x~
~ ~ , ' ' !~ llo lwoolwoo~ ~w ~ U~ ~
~. ~ ~ _ o o ! o ~ ~ i ~ n o ~ o Ul co 1 ~
! I I ~o~n --., , I ,~
o o 1~ o ~ n o ~n ~ ~~~ , t , ~
~ fD ~ co ~ P ao ~ Ico ICD co co jc~ co ~ c~ o tD ~
rl ~' (D P' ~ l l l l :~S ~ ~ ~ -,t ~t (D ~ ~D O ,~ w ~ w 1~ i~r~3 oZ
t 1~- ~ o ~ ~ o o ~
lo ~o X ~ i i 3 ~ ~D
@ i I l ¦ ~0 pJ I I I 1. _ ~~ 1, , . I~ 0~
~. ~ O O 10 o o 10 IC~ O O 10 0 0 0 dP ~
~ ll ll ll ll l ll l ll u~
I I . I I . _ Le A 20 848 Exam~les 14 to 19 AsS graft polymer is mixed with molten polyalkylene terephthalate in a screw analogously to Examples 1 to 13. Glass fibres are then metered into this melt and are homogeneously dis-tributed. Test bodies were produced from the granulated material as in Examples 1 to 13. The impact and falling ball test accord-ing to DIN 53 443, as illustrated in Figure 3 gives a reliable idea of the strength of the reinforced mixtures under impact strain.
In Figure 3, the ball 4 ~as a radius of 25 mm.
(a) denotes the impact point of the ball, (b) denotes the rod feed (~ approximately 4 mm) in the middle of the base surface, and (c) deontes a test point parallel to (a).
There is a prerequisite that the test bodies have as low an orientation degree as possible, such as the small test box illustrated in Figures 1 and 2 wh~ch has a height of 1 of 4Q mm, a width 2 of 46.7 ~ and a length 3 of 106.7 mm or 3l of 120 mm and a wall thickness 5 of 1.5 m~.
rY . T ~ _ 0~ ~
_~ ~ ~ a~ oo u~ ~
~ ~ ~ l` ~ ~ ~ ~ O
~ e ~--.
~ ~
0 0 a~ ~ 3 h R
. ~ -~ ~a (d 0 O ~ ~ ~ ~ O l~ O ~ O
Z ~ ~ q ~ .
S
0 ~ ~ c~
~ ~ 1~ ~ ~
H ta _ .
I_ O O O O O O O
O O
.~ . _ G~
Q ~
o o o o o o m o _~ ~ ~ ~ ~ ~
to ~ ~
m ~ ~ ~ I~ ~
a) ~ ~ ~ ~ o o X ~ _ . . .
U~
~-~1 0 ~ ~ ~ t~ Cl 3 _ .
O ~ ~
,l ~Q -I _ ~ O ~
a ~q 0 a~ a~ o O
o~
o ~ m--HH . _ . _ O
a X
Le A 20 848
The weld line strength was tested (in the tensile strength test according to DIN 53 455) using tensile test bars injection-moulded at both ends.
Le A 20 848 3~
g ~3 ~3 (D
_ tD
_~ ~ H
H (D
H It --~ G~
. ~ pJ
~t ~h r~
~¢ (D ~
P~ O
co CO ~ ~h O ~_ O O U~ ~h ~
(D
O O
~ ^W
W ~
--(D
(D
~Q tD
Q
l_ ,_ ~ ~ O
c ~o ~ r~
J.
~-I~
O~ ~
~ ~h CO ~I ~I
CC~ N ~ It m ,_ -GS
Hl ~' o o o ~
I_ O ~n tD
tD
G~
Le A 20 848 W ~ O ~ , x 0~ j I 1- H
_ I 11 4 o !~ ~o~
o~
~ 3 , ~
ll I l ll x~
~ ~ , ' ' !~ llo lwoolwoo~ ~w ~ U~ ~
~. ~ ~ _ o o ! o ~ ~ i ~ n o ~ o Ul co 1 ~
! I I ~o~n --., , I ,~
o o 1~ o ~ n o ~n ~ ~~~ , t , ~
~ fD ~ co ~ P ao ~ Ico ICD co co jc~ co ~ c~ o tD ~
rl ~' (D P' ~ l l l l :~S ~ ~ ~ -,t ~t (D ~ ~D O ,~ w ~ w 1~ i~r~3 oZ
t 1~- ~ o ~ ~ o o ~
lo ~o X ~ i i 3 ~ ~D
@ i I l ¦ ~0 pJ I I I 1. _ ~~ 1, , . I~ 0~
~. ~ O O 10 o o 10 IC~ O O 10 0 0 0 dP ~
~ ll ll ll ll l ll l ll u~
I I . I I . _ Le A 20 848 Exam~les 14 to 19 AsS graft polymer is mixed with molten polyalkylene terephthalate in a screw analogously to Examples 1 to 13. Glass fibres are then metered into this melt and are homogeneously dis-tributed. Test bodies were produced from the granulated material as in Examples 1 to 13. The impact and falling ball test accord-ing to DIN 53 443, as illustrated in Figure 3 gives a reliable idea of the strength of the reinforced mixtures under impact strain.
In Figure 3, the ball 4 ~as a radius of 25 mm.
(a) denotes the impact point of the ball, (b) denotes the rod feed (~ approximately 4 mm) in the middle of the base surface, and (c) deontes a test point parallel to (a).
There is a prerequisite that the test bodies have as low an orientation degree as possible, such as the small test box illustrated in Figures 1 and 2 wh~ch has a height of 1 of 4Q mm, a width 2 of 46.7 ~ and a length 3 of 106.7 mm or 3l of 120 mm and a wall thickness 5 of 1.5 m~.
rY . T ~ _ 0~ ~
_~ ~ ~ a~ oo u~ ~
~ ~ ~ l` ~ ~ ~ ~ O
~ e ~--.
~ ~
0 0 a~ ~ 3 h R
. ~ -~ ~a (d 0 O ~ ~ ~ ~ O l~ O ~ O
Z ~ ~ q ~ .
S
0 ~ ~ c~
~ ~ 1~ ~ ~
H ta _ .
I_ O O O O O O O
O O
.~ . _ G~
Q ~
o o o o o o m o _~ ~ ~ ~ ~ ~
to ~ ~
m ~ ~ ~ I~ ~
a) ~ ~ ~ ~ o o X ~ _ . . .
U~
~-~1 0 ~ ~ ~ t~ Cl 3 _ .
O ~ ~
,l ~Q -I _ ~ O ~
a ~q 0 a~ a~ o O
o~
o ~ m--HH . _ . _ O
a X
Le A 20 848
Claims (17)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A polymer composition consisting of:
(A) from 65 to 99% by weight, of polyalkylene terephthalate which consists of:
(a) from 1 to 100% by weight of polyethylene terephthalate; and (b) from 99 to 0% by weight of polybutylene terephthalate; and (B) from 1 to 35% by weight of ABS grafted polymer, the percent-ages of (A) and (B) being based on the sum of (A) + (B) and the percentages of (a) and (b) being based on (A), and the graft polymer (s) being obtained by a grafting reaction of:
(I) from 10 to 40% by weight based on (B) of a mixture consisting of:
(a) from 10 to 35% by weight based on the total of (a) + (b), of acrylonitrile, and (b) from 65 to 90% by weight based on the sum of (a) + (b), of styrene; on (II) from 60 to 90% by weight based on (B) of a crosslinked butadiene polymer containing at least 70% by weight based on (II) of butadiene radicals as the graft base;
wherein the gel content of the graft base (II) is at least 70%
(measured in toluene), the grafting degree of the graft polymer (G) is from 0.15 to 0.55 and the average particle diameter d50 of the ABS graft polymer (B) is from 0.2 to 0.6 µm.
(A) from 65 to 99% by weight, of polyalkylene terephthalate which consists of:
(a) from 1 to 100% by weight of polyethylene terephthalate; and (b) from 99 to 0% by weight of polybutylene terephthalate; and (B) from 1 to 35% by weight of ABS grafted polymer, the percent-ages of (A) and (B) being based on the sum of (A) + (B) and the percentages of (a) and (b) being based on (A), and the graft polymer (s) being obtained by a grafting reaction of:
(I) from 10 to 40% by weight based on (B) of a mixture consisting of:
(a) from 10 to 35% by weight based on the total of (a) + (b), of acrylonitrile, and (b) from 65 to 90% by weight based on the sum of (a) + (b), of styrene; on (II) from 60 to 90% by weight based on (B) of a crosslinked butadiene polymer containing at least 70% by weight based on (II) of butadiene radicals as the graft base;
wherein the gel content of the graft base (II) is at least 70%
(measured in toluene), the grafting degree of the graft polymer (G) is from 0.15 to 0.55 and the average particle diameter d50 of the ABS graft polymer (B) is from 0.2 to 0.6 µm.
2. A composition according to claim 1, which consists of from 70 to 98% by weight of (A) and from 2 to 30% by weight of (B).
3. A composition according to claim 1, which consists of from 75 to 97% by weight of (A) and from 3 to 25% by weight of (B).
4. A composition according to claim 1, wherein the polyalkyl-eneterephthalate (A) consists of from 10 to 80% by weight of poly-ethyleneterephthalate and of from 90 to 20% by weight of poly-butyleneterephthalate.
5. A composition according to claim 2 or 3, wherein the poly-alkyleneterephthalate (A) consists of from 10 to 80% by weight of polyethyleneterephthalate and of from 90 to 20% by weight of polybutyleneterephthalate.
6. A composition according to claim 1, wherein the polyalkyl-eneterephthalate (A) consists of from 30 to 50% by weight of polyethylene terephthalate and of from 70 to 40% by weight of polybutyleneterephthalate.
7. A composition according to claim 2 or 3, wherein the polyalkyleneterephthalate (A) consists of from 30 to 60% by weight of polyethylene terephthalate and of from 70 to 40% by weight of polybutyleneterephthalate.
8. A composition according to claim 1, 2 or 3, wherein the fraft polymer (B) is obtained by a grafting reaction of from 10 to 35% by weight of (I) on from 65 to 90% by weight of (II).
9. A composition according to claim 4 or 6, wherein the graft polymer (B) is obtained by a grafting reaction of from 10 to 35%
by weight of (I) on from 65 to 90% by weight of (II).
by weight of (I) on from 65 to 90% by weight of (II).
10. A composition according to claim 1, 2 or 3, wherein the graft polymer (B) is obtained by a grafting reaction of from 15 to 25% by weight of (I) on from 75 to 85% by weight, of (II).
11. A composition according to claim 1, 2 or 3, wherein the graft monomer mixture (I) consists of from 20 to 35% by weight of acrylonitrile and from 65 to 80% by weight of styrene.
12. A composition according to claim 4 or 6, wherein the graft monomer mixture (I) consists of from 20 to 35% by weight of acrylonitrile and from 65 to 85% by weight of styrene.
13. A composition according to claim 1, 2 or 3, wherein the gel content of the graft base (II) is at least 80% (measured in toluene).
14. A composition according to claim 1, 2 or 3, wherein the average particle diameter d50 of the graft polymer (B) is from 0.3 to 0-5 µm.
15. A composition according to claim 1, 2 or 3, wherein the average particle diameter d50 of the graft polymer (B) is about 0.4 µm.
16. A moulding compound which comprises a reinforcing material and a polymer composition as defined in claim 1, 2 or 3, wherein the amount of the reinforcing material is from 5 to 60% by weight based on the sum of the reinforcing material and the polymer composition.
17. A moulding compound which comprises a reinforcing material and a polymer composition as defined in claim 4 or 5, wherein the amount of the reinforcing material is from 5 to 60% by weight based on the sum of the reinforcing material and the polymer composition.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3100902.6 | 1981-01-14 | ||
| DE19813100902 DE3100902A1 (en) | 1981-01-14 | 1981-01-14 | HIGH IMPACT TOE POLYALKYLENE TEREPHTHALATE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1176390A true CA1176390A (en) | 1984-10-16 |
Family
ID=6122583
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000394001A Expired CA1176390A (en) | 1981-01-14 | 1982-01-12 | High impact resistant composition including polyethylene terephthalates and abs grafted polymer |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0056243B1 (en) |
| JP (1) | JPS57137350A (en) |
| CA (1) | CA1176390A (en) |
| DE (2) | DE3100902A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4753986A (en) * | 1986-12-22 | 1988-06-28 | General Electric Company | Polyester compositions having high impact strength |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3339001A1 (en) * | 1983-07-06 | 1985-01-17 | Bayer Ag, 5090 Leverkusen | THERMOPLASTIC POLYESTER MOLDS WITH HIGH TOUGHNESS |
| DE3576965D1 (en) * | 1984-09-15 | 1990-05-10 | Huels Chemische Werke Ag | MOLDS BASED ON THERMOPLASTICS. |
| DE3504986A1 (en) * | 1985-02-14 | 1986-08-14 | Hüls AG, 4370 Marl | MOLDING MATERIALS BASED ON LINEAR, HIGH MOLECULAR POLYESTERS |
| JPS61207456A (en) * | 1985-03-11 | 1986-09-13 | Daicel Chem Ind Ltd | Thermoplastic resin composition |
| DE3535985A1 (en) * | 1985-10-09 | 1987-04-09 | Bayer Ag | MINERAL-FILLED THERMOPLASTIC POLYESTER, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS MOLDS |
| AU619374B2 (en) * | 1989-02-16 | 1992-01-23 | General Electric Company | Polyesters modified with abs terpolymers |
| JPH03202477A (en) * | 1989-12-28 | 1991-09-04 | Mitsubishi Rayon Co Ltd | Plated article |
| DE4339983A1 (en) * | 1993-11-24 | 1995-06-01 | Agfa Gevaert Ag | Molded plastic article |
| US8168707B2 (en) * | 2008-01-15 | 2012-05-01 | Sabic Innovative Plastics Ip B.V. | Moldable polyester compositions, processes of manufacture, and articles thereof |
| US8791189B2 (en) * | 2008-01-15 | 2014-07-29 | Sabic Innovative Plastics Ip B.V. | Moldable polyester compositions, processes of manufacture, and articles thereof |
| KR100950217B1 (en) * | 2009-08-28 | 2010-03-29 | (주)애린엠피테크 | Manufacturing method of composite formed article |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5033832B2 (en) * | 1971-09-17 | 1975-11-04 | ||
| IT963692B (en) * | 1972-08-03 | 1974-01-21 | Montedison Spa | SHOCK-RESISTANT POLYESTERS |
| CA1062390A (en) * | 1975-08-11 | 1979-09-11 | William Steffancin | Amorphous polyester graft polymer alloys |
| JPS5457563A (en) * | 1977-10-17 | 1979-05-09 | Toray Ind Inc | Thermoplastic resin composition |
| US4280949A (en) * | 1979-02-12 | 1981-07-28 | General Electric Company | Modified polyester compositions containing mineral filler |
| DE2927576A1 (en) * | 1979-07-07 | 1981-01-15 | Bayer Ag | HIGH IMPACT POLYBUTYLENE TEREPHTHALATE |
-
1981
- 1981-01-14 DE DE19813100902 patent/DE3100902A1/en not_active Withdrawn
-
1982
- 1982-01-07 DE DE8282100044T patent/DE3265676D1/en not_active Expired
- 1982-01-07 EP EP82100044A patent/EP0056243B1/en not_active Expired
- 1982-01-12 CA CA000394001A patent/CA1176390A/en not_active Expired
- 1982-01-12 JP JP57002364A patent/JPS57137350A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4753986A (en) * | 1986-12-22 | 1988-06-28 | General Electric Company | Polyester compositions having high impact strength |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0056243B1 (en) | 1985-08-28 |
| EP0056243A1 (en) | 1982-07-21 |
| JPS57137350A (en) | 1982-08-24 |
| DE3100902A1 (en) | 1982-08-05 |
| DE3265676D1 (en) | 1985-10-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4292233A (en) | High-impact polybutylene terephthalate | |
| CA1166388A (en) | Thermoplastic polyester moulding compositions containing grafted polyacrylates | |
| US4172859A (en) | Tough thermoplastic polyester compositions | |
| US4397986A (en) | Thermoplastic polyester blends | |
| US4417026A (en) | Thermoplastic polyester moulding compositions having improved toughness | |
| JPS59131649A (en) | Reinforced multi-phase thermoplastic composition | |
| CA1176390A (en) | High impact resistant composition including polyethylene terephthalates and abs grafted polymer | |
| EP0114288A2 (en) | Additive concentrate for polyester compositions and method of addition | |
| US4666972A (en) | Thermoplastic moulding compositions based on polyalkylene terephthalate and polymer and a process for the production thereof | |
| EP0519098B1 (en) | Aromatic carbonate polymer based blend with low gloss | |
| US4547547A (en) | Polymer blends | |
| JPH0449579B2 (en) | ||
| EP0042724B1 (en) | Polyethylene terephthalate blends | |
| US4281079A (en) | Polyarylene ester compositions | |
| JPH0232143A (en) | Thermoplastic resin composition | |
| JPH02105848A (en) | Impact-resistant thermoplastic molding compound made of aromatic polyester-carbonate and polyalkylene terephthalate | |
| EP0386546A2 (en) | Thermoplastic molding compositions | |
| EP0357459B1 (en) | Moldable styrene-maleic anhydride/polybutylene terephthalate composition | |
| US5118805A (en) | Phosphoroustrislactams and methods for their production | |
| US4096200A (en) | N-Alkyl polyurethane/vinyl polymer mixtures | |
| JPS62209157A (en) | Thermoplastic resin composition | |
| JPS62129350A (en) | Thermoplastic resin composition | |
| US5086113A (en) | Thermoplastic blends of ABS containing ethylene terpolymers | |
| EP0427268B1 (en) | Thermoplastic compositions based on vinyl-aromatic copolymers and polyamide resins | |
| CA1317049C (en) | Polycarbonate composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEC | Expiry (correction) | ||
| MKEX | Expiry |