CA2014836A1 - Polyolefin molding compound - Google Patents
Polyolefin molding compoundInfo
- Publication number
- CA2014836A1 CA2014836A1 CA002014836A CA2014836A CA2014836A1 CA 2014836 A1 CA2014836 A1 CA 2014836A1 CA 002014836 A CA002014836 A CA 002014836A CA 2014836 A CA2014836 A CA 2014836A CA 2014836 A1 CA2014836 A1 CA 2014836A1
- Authority
- CA
- Canada
- Prior art keywords
- molding compound
- polyolefin molding
- phosphonate
- calcium
- alkyl group
- 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.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
Abstract
Abstract of the Disclosure Polyolefin molding compound During the processing of 1-olefin homopolymers and co-polymers, the corrosion on the processing machinery is reduced if a phosphonate of the formula
Description
HOECHST AKTIENGESELLSCHAFT HOE 89/F 124 D~. DA
Description ~Ol~B36 Polyolefin molding compound The invention relates to a polyolefin molding compound which i8 less corrosive toward~ the processing machinery while it is being proces3ed.
When polyolefin molding compounds are proces~ed to form moldings, corrosion freguently occurs on the metal parts which come into contact with the hot molding compound.
There has therefore been no lack of attempts to eliminate this deficiency.
It is known to add zinc stearate or calcium stearate to such molding compounds in order to reduce the corrosion on the processing machinery. However, during proce6sing, unde3irable deposits are formed on machine parts and/or vapors are produced, resulting in production difficul-ties~ When the moldings are cooled with water, water carry-over occurs. The result of this effect i8 to reduce the surface quality and disturb production.
It is further known to use inorganic substances, such as hydrotalcites of the type Mg~.~al2(0H)3CO3.3.5H20, to prevent corrosion. Such pulverulent inorganic additives are not easy to incorporate into polyolefins, however, and they also lead to quality-reducing hard spots, which cause ma~or defects especially in the case of transparent shaped articles. Furthermore, the color quality is impaired (yellowing) when hydrotalcites are used.
It has now been found that a polyolefin molding compound containing n very small amount of a special phosphonate is less corrosive towards the machine parts while it is being processed on machinery.
The invention thus relates to a polyolefin molding com-pound consisting of a homopolymer or copolymer of a 1-'~;. ' - , . .
_ 2 - 2~4~3~
slefin having 2 ~o 10 carbon atom~ and 0.001 to 0.5~ by weight, based on the polyolefin, of a phoqphonate of the formula ~HO~ 2)n-P-OR3 IM2 1 in which Rl and R2 are identical or different and are a hydrogen atom or a linear or branched C~-C~ alkyl group, R3 is a linear Cl-C~ alkyl group, n i~ 1, 2, 3 or 4 and M
iB zinc, magnesium, calcium, barium or lead.
Base polymers which are suitable for the polyolefin molding compound according to the invention are homo-polymers or copolymers of l-olefins having 2 to 10 carbon atoms, for example ethylene, propylene, but-l-ene and 4-methylpent-l-ene, possible polymers thus being poly-ethylene, polypropylene, polybut-1-ene, poly-4-methyl~
pent-l-ene, ethylene/propylene copolymers, ethylene/
propylene/butylene copolymers, propylene/butylene co-polymQrs, ethylene/butylene copolymers and mixtures of these polymers. It is preferred to use propylene poly-mers, especially propylene homopolymers. The polymer constitutes 99.5 to 99.999% by weight of the molding compound.
The phosphonate used in the molding compound has the formuln [ O ~ 1 --~ Z~ 6 in which Rl and R2 are identical or different and are a hydrogen atom or a linear or branched Cl-C6 alkyl group, for example methyl, ethyl, t-butyl or i-amyl, preferably t-butyl, R3 iB a linear Cl-C6 alkyl group, for example methyl, ethyl, propyl, butyl or amyl, n is 1, 2, 3 or 4 and M is zinc, magnesium, calcium, barium or lead, pre-ferably calcium.
Of the phosphonates to be used according to the inven-tion, the maqnesium and calcium phosphonates are pre-ferred. A calcium bis(monoalkyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate) or magnesium bis(monoalkyl-3,5-di-tert-butyl-4-hydroxybenzylpho~phonate) i~ used in par-ticular. The amount of phosphonate is 0.001 to 0.5 and preferably 0.01 to 0.04% by weight, based on the poly-olefin.
The molding compound according to the invention can con-tain the conventional additives for facilitating pro-ce~sing and improving the physical properties. The following additives may be mentioned: antioxidants, anti-` 20 stat~c agents, lubricants, nucleating agents, anti-j blocking agents and fillers (organic and/or inorganic)~
color pigments, dyeq, synthetic and natural resins and flame retardants. The first group is generally pre~ent in the molding compound in an amount of 0.1 to 5% by j 25 weight, based on the amount of polymer (+ filler).
Fillers, color pigments, synthetic and natural resins and flame retardants are used in an amount appropriate to the current requirements.
The phosphonate i8 incorporated into the polyolefin in known manner, for example by means of a mixer, extruder, roll or kn~ader, especially by means of a twin-screw kneader, it also being possible to incorporate the phos-phonate as a masterbatch. Conventional carriers are suitable as masterbatch carriers, for example those ba~ed on PE or PP wax. The phosphonate is preferably incor-porated in such a way that it melts during the incorpor "
' ~ . .
r' . ~
- 4 - Z~ 3~
ation proces~.
The molding compound according to the invention is u~ed for transparent 6haped articles, for example sheets/
films, cups, bottles or filaments During proce~sing of this molding compound, the corrosion on the processing machinery was exceptionally slight, no water was carried over from the quenching tanX and no deposits or exudates were observed.
The following Examples are intended to illustrate the invention.
Examples 1 and 2 and Comparative ~xamples A to D
Different amounts of calcium bis(monoethyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate) were incorporated into polypropylene powder (melt flow index 2.16/230 4.5 g/10 min - proportion insoluble in n-heptane 96% by weight -melting point 165C) by means of an extruder.
In the Comparative Examples, different amounts of calcium stearate were incorporated instead of the calcium bis-(monoethyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate).
In all the experiments, 0.1~ by weight of pentaerythrityl tetrakis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate) was used to stabilize the polypropylene.
To determine the corrosiveness of the materials, two 0.2 mm thick ~trips of iron were placed in each of the samples of molding compound 80 as to be uniformly sur-rounded by the molding compound. To do this, about half of the weighed amounts of material (6 g) was introduced into the recess (~ 50 mm) in 8 4 mm spacer frame and the strips were laid next to one another with tweezers 80 as not to touch each other or the frame. The ~trips of iron were ca. 20 mm long and were stored in acetone after having bsen degreased by rubbing in acetone. Before 483~
being placed in the ~amples, they were freed of acetone with a ~oft cloth. The strips of iron must not be touched with the fingers.
The spacer frame~ and cover ~heets (aluminum sheets) were placed in a press heated to 250C and, after a contact time of 5 min, compressed for 1 h under a pressure of 100 bar. The 0.5 mm thick aluminum sheet, in~erted betw~en the cover plate and the spacer frame, had previously been rubbed with petroleum ~elly in order to reduce the ad-hesion of the product to the aluminum sheet. The presswas then immediately cooled. The strips of iron must still be lying next to one another and must not be pro-~ecting out of the slab. They were punched out of the slab, perforated and weighed accurately to within 1/10 mg. Naturally they must not be touched with the hands.
They were then hung in rows on a copper wire in the steam produced by boiling water. There was a sieve above the surface of the water in order to prevent water droplets from settling on the strips. After 1 h, the strips of iron were removed, stored at room temperature for 1 h and then reweighed. The corrosivenesB iB given by the per-centage increase in weight.
The appearance of deposits/exudates and water carry-over was assessed during processing of the molding compounds on a high-performance tape producing plant with water cooling. The haul-off speed was 40 m/min for all the processing experiments. In the case of flat-film producing plants with water cooling, deposlts/exudates and especially water carry-over with the primary film represent a substantial qualitative deficiency. The appearance of deposits/exudates and water carry-over detract from the economics. In particular, water carry-over results in an increased tear rate, i.e. an increase in the number of times the film tears per unit production time. Mor~ detailed data on the Examples and Comparative Examplez, and their assessment, can be found in the TablQ .
.~ , . . , ~ . :
æ~
Z0~48;36 Example/ Wl W2 Corrosive- Water Deposits/
Comparative [X by [X by ness carrg-over exudates Example weight] weight]
1 0.02 - 0.11none ++
Description ~Ol~B36 Polyolefin molding compound The invention relates to a polyolefin molding compound which i8 less corrosive toward~ the processing machinery while it is being proces3ed.
When polyolefin molding compounds are proces~ed to form moldings, corrosion freguently occurs on the metal parts which come into contact with the hot molding compound.
There has therefore been no lack of attempts to eliminate this deficiency.
It is known to add zinc stearate or calcium stearate to such molding compounds in order to reduce the corrosion on the processing machinery. However, during proce6sing, unde3irable deposits are formed on machine parts and/or vapors are produced, resulting in production difficul-ties~ When the moldings are cooled with water, water carry-over occurs. The result of this effect i8 to reduce the surface quality and disturb production.
It is further known to use inorganic substances, such as hydrotalcites of the type Mg~.~al2(0H)3CO3.3.5H20, to prevent corrosion. Such pulverulent inorganic additives are not easy to incorporate into polyolefins, however, and they also lead to quality-reducing hard spots, which cause ma~or defects especially in the case of transparent shaped articles. Furthermore, the color quality is impaired (yellowing) when hydrotalcites are used.
It has now been found that a polyolefin molding compound containing n very small amount of a special phosphonate is less corrosive towards the machine parts while it is being processed on machinery.
The invention thus relates to a polyolefin molding com-pound consisting of a homopolymer or copolymer of a 1-'~;. ' - , . .
_ 2 - 2~4~3~
slefin having 2 ~o 10 carbon atom~ and 0.001 to 0.5~ by weight, based on the polyolefin, of a phoqphonate of the formula ~HO~ 2)n-P-OR3 IM2 1 in which Rl and R2 are identical or different and are a hydrogen atom or a linear or branched C~-C~ alkyl group, R3 is a linear Cl-C~ alkyl group, n i~ 1, 2, 3 or 4 and M
iB zinc, magnesium, calcium, barium or lead.
Base polymers which are suitable for the polyolefin molding compound according to the invention are homo-polymers or copolymers of l-olefins having 2 to 10 carbon atoms, for example ethylene, propylene, but-l-ene and 4-methylpent-l-ene, possible polymers thus being poly-ethylene, polypropylene, polybut-1-ene, poly-4-methyl~
pent-l-ene, ethylene/propylene copolymers, ethylene/
propylene/butylene copolymers, propylene/butylene co-polymQrs, ethylene/butylene copolymers and mixtures of these polymers. It is preferred to use propylene poly-mers, especially propylene homopolymers. The polymer constitutes 99.5 to 99.999% by weight of the molding compound.
The phosphonate used in the molding compound has the formuln [ O ~ 1 --~ Z~ 6 in which Rl and R2 are identical or different and are a hydrogen atom or a linear or branched Cl-C6 alkyl group, for example methyl, ethyl, t-butyl or i-amyl, preferably t-butyl, R3 iB a linear Cl-C6 alkyl group, for example methyl, ethyl, propyl, butyl or amyl, n is 1, 2, 3 or 4 and M is zinc, magnesium, calcium, barium or lead, pre-ferably calcium.
Of the phosphonates to be used according to the inven-tion, the maqnesium and calcium phosphonates are pre-ferred. A calcium bis(monoalkyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate) or magnesium bis(monoalkyl-3,5-di-tert-butyl-4-hydroxybenzylpho~phonate) i~ used in par-ticular. The amount of phosphonate is 0.001 to 0.5 and preferably 0.01 to 0.04% by weight, based on the poly-olefin.
The molding compound according to the invention can con-tain the conventional additives for facilitating pro-ce~sing and improving the physical properties. The following additives may be mentioned: antioxidants, anti-` 20 stat~c agents, lubricants, nucleating agents, anti-j blocking agents and fillers (organic and/or inorganic)~
color pigments, dyeq, synthetic and natural resins and flame retardants. The first group is generally pre~ent in the molding compound in an amount of 0.1 to 5% by j 25 weight, based on the amount of polymer (+ filler).
Fillers, color pigments, synthetic and natural resins and flame retardants are used in an amount appropriate to the current requirements.
The phosphonate i8 incorporated into the polyolefin in known manner, for example by means of a mixer, extruder, roll or kn~ader, especially by means of a twin-screw kneader, it also being possible to incorporate the phos-phonate as a masterbatch. Conventional carriers are suitable as masterbatch carriers, for example those ba~ed on PE or PP wax. The phosphonate is preferably incor-porated in such a way that it melts during the incorpor "
' ~ . .
r' . ~
- 4 - Z~ 3~
ation proces~.
The molding compound according to the invention is u~ed for transparent 6haped articles, for example sheets/
films, cups, bottles or filaments During proce~sing of this molding compound, the corrosion on the processing machinery was exceptionally slight, no water was carried over from the quenching tanX and no deposits or exudates were observed.
The following Examples are intended to illustrate the invention.
Examples 1 and 2 and Comparative ~xamples A to D
Different amounts of calcium bis(monoethyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate) were incorporated into polypropylene powder (melt flow index 2.16/230 4.5 g/10 min - proportion insoluble in n-heptane 96% by weight -melting point 165C) by means of an extruder.
In the Comparative Examples, different amounts of calcium stearate were incorporated instead of the calcium bis-(monoethyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate).
In all the experiments, 0.1~ by weight of pentaerythrityl tetrakis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate) was used to stabilize the polypropylene.
To determine the corrosiveness of the materials, two 0.2 mm thick ~trips of iron were placed in each of the samples of molding compound 80 as to be uniformly sur-rounded by the molding compound. To do this, about half of the weighed amounts of material (6 g) was introduced into the recess (~ 50 mm) in 8 4 mm spacer frame and the strips were laid next to one another with tweezers 80 as not to touch each other or the frame. The ~trips of iron were ca. 20 mm long and were stored in acetone after having bsen degreased by rubbing in acetone. Before 483~
being placed in the ~amples, they were freed of acetone with a ~oft cloth. The strips of iron must not be touched with the fingers.
The spacer frame~ and cover ~heets (aluminum sheets) were placed in a press heated to 250C and, after a contact time of 5 min, compressed for 1 h under a pressure of 100 bar. The 0.5 mm thick aluminum sheet, in~erted betw~en the cover plate and the spacer frame, had previously been rubbed with petroleum ~elly in order to reduce the ad-hesion of the product to the aluminum sheet. The presswas then immediately cooled. The strips of iron must still be lying next to one another and must not be pro-~ecting out of the slab. They were punched out of the slab, perforated and weighed accurately to within 1/10 mg. Naturally they must not be touched with the hands.
They were then hung in rows on a copper wire in the steam produced by boiling water. There was a sieve above the surface of the water in order to prevent water droplets from settling on the strips. After 1 h, the strips of iron were removed, stored at room temperature for 1 h and then reweighed. The corrosivenesB iB given by the per-centage increase in weight.
The appearance of deposits/exudates and water carry-over was assessed during processing of the molding compounds on a high-performance tape producing plant with water cooling. The haul-off speed was 40 m/min for all the processing experiments. In the case of flat-film producing plants with water cooling, deposlts/exudates and especially water carry-over with the primary film represent a substantial qualitative deficiency. The appearance of deposits/exudates and water carry-over detract from the economics. In particular, water carry-over results in an increased tear rate, i.e. an increase in the number of times the film tears per unit production time. Mor~ detailed data on the Examples and Comparative Examplez, and their assessment, can be found in the TablQ .
.~ , . . , ~ . :
æ~
Z0~48;36 Example/ Wl W2 Corrosive- Water Deposits/
Comparative [X by [X by ness carrg-over exudates Example weight] weight]
1 0.02 - 0.11none ++
2 0.04 - O.06none +~
A - O.02 0.26~ubstantial --B - 0.04 0.21substantial --C - O.08 0.133ubstantial --D - - O.30none ++
Wl - amount of calcium bis(monoethyl-3,5-di-t-butyl-4-hydroxybenzyl-phosphonate) added W2 = amount of calcium stearate added The corrosiveness must be less than 0.15. 5 ++ production not disturbed by deposits/exudates to the extent that cleaning work is required -- di~turbing deposits/exudates causing interruptions in production None of the primary films (Examples and Co~parative Examples A to D) showed hard spots other than isolated lumps of gel particles.
A - O.02 0.26~ubstantial --B - 0.04 0.21substantial --C - O.08 0.133ubstantial --D - - O.30none ++
Wl - amount of calcium bis(monoethyl-3,5-di-t-butyl-4-hydroxybenzyl-phosphonate) added W2 = amount of calcium stearate added The corrosiveness must be less than 0.15. 5 ++ production not disturbed by deposits/exudates to the extent that cleaning work is required -- di~turbing deposits/exudates causing interruptions in production None of the primary films (Examples and Co~parative Examples A to D) showed hard spots other than isolated lumps of gel particles.
Claims (6)
1. A polyolefin molding compound consisting of a homo-polymer or copolymer of a 1-olefin having 2 to 10 carbon atoms and 0.001 to 0.5% by weight, based on the polyole-fin, of a phosphonate of the formula in which R1 and R2 are identical or different and are a hydrogen atom or a linear or branched C1-C6 alkyl group, R3 is a linear C1-C6 alkyl group, n is 1, 2, 3 or 4 and is zinc, magnesium, calcium, barium or lead.
2. A polyolefin molding compound as claimed in claim 1, wherein the 1-olefin polymer is polypropylene, polyethy-lene or a propylene/1-olefin polymer with ethylene or butylene as the 1-olefin.
3. A polyolefin molding compound as claimed in claim 1, wherein the phosphonate is calcium or magnesium bis(mono-ethyl-3,5-di-t-butyl-4- hydroxybenzylphosphonate).
4. Use of the polyolefin molding compound as claimed in claim 1 for the manufacture of transparent shaped articles.
5. A process for reducing the corrosion on machinery during the processing of homopolymers or copolymers of a 1-olefin having 2 to 10 carbon atoms, which comprises adding 0.001 to 0.05% by weight of a phosphonate of the formula in which R1 and R2 are identical or different and are a hydrogen atom or a linear or branched C1-C6 alkyl group, R3 is a linear C1-C6 alkyl group, n is 1, 2, 3 or 4 and 18 zinc, magnesium, calcium, barium or lead.
6. The compound as claimed in claim 1 and substantially as described herein.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3912825.3 | 1989-04-19 | ||
| DE3912825A DE3912825A1 (en) | 1989-04-19 | 1989-04-19 | POLYOLEFIN MOLD |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2014836A1 true CA2014836A1 (en) | 1990-10-19 |
Family
ID=6378982
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002014836A Abandoned CA2014836A1 (en) | 1989-04-19 | 1990-04-18 | Polyolefin molding compound |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0393518A2 (en) |
| JP (1) | JPH02296845A (en) |
| AU (1) | AU5328590A (en) |
| CA (1) | CA2014836A1 (en) |
| DE (1) | DE3912825A1 (en) |
| ZA (1) | ZA902919B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997007158A1 (en) * | 1995-08-15 | 1997-02-27 | Hoechst Celanese Corporation | Improved waxes for actuators |
-
1989
- 1989-04-19 DE DE3912825A patent/DE3912825A1/en not_active Withdrawn
-
1990
- 1990-04-12 EP EP90107056A patent/EP0393518A2/en not_active Withdrawn
- 1990-04-17 AU AU53285/90A patent/AU5328590A/en not_active Abandoned
- 1990-04-18 JP JP2100558A patent/JPH02296845A/en active Pending
- 1990-04-18 ZA ZA902919A patent/ZA902919B/en unknown
- 1990-04-18 CA CA002014836A patent/CA2014836A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| ZA902919B (en) | 1991-01-30 |
| EP0393518A2 (en) | 1990-10-24 |
| DE3912825A1 (en) | 1990-10-25 |
| JPH02296845A (en) | 1990-12-07 |
| AU5328590A (en) | 1990-10-25 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |