CN1344289A - Olefin polymer compsn. having low smoke generation and fiber, film and fabric prepared therefrom - Google Patents
Olefin polymer compsn. having low smoke generation and fiber, film and fabric prepared therefrom Download PDFInfo
- Publication number
- CN1344289A CN1344289A CN00805156A CN00805156A CN1344289A CN 1344289 A CN1344289 A CN 1344289A CN 00805156 A CN00805156 A CN 00805156A CN 00805156 A CN00805156 A CN 00805156A CN 1344289 A CN1344289 A CN 1344289A
- Authority
- CN
- China
- Prior art keywords
- polymer composition
- acid ester
- phosphorous acid
- amine oxide
- tert
- 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.)
- Pending
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
- C08K5/16—Nitrogen-containing compounds
- C08K5/32—Compounds containing nitrogen bound to oxygen
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- 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
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- 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
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
Abstract
A polymer composition and fiber or film prepared therefrom, which contains i) an olefin polymer containing an acid neutralizing agent other than a metallic salt of a saturated or unsaturated fatty acid, and ii) a stabilizer system distributed throughout the polymer, the stabilizer system including (a) a phosphite selected from 2,2',2''-nitrilo[triethyl-tris(3,3',5,5'-tetra-tert-butyl-1,1-biphenyl-2,2'-diyl)phosphite] and tris(2,4-di-tert-butylphenyl) phosphite; and (b) a saturated hydrocarbon amine oxide. Also disclosed is a method for preparing a polyolefin fiber or film, which includes adding the above stabilizer system to an olefin polymer containing such an acid neutralizing agent. In a special embodiment, an unconventionally low amount of a saturated or unsaturated fatty acid may be present as a processing aid.
Description
The background of invention
Polyolefine especially polypropylene usually by with molten polymer from nib for example the die head of spinning jet, film or sheet material extrude, and the long filament of quenching molten state, film or sheet material, make long filament, film or sheet material orientation, and before being rolled onto on the bobbin, make long filament, film or the sheet material heat setting type of orientation, thereby form fiber, film or sheet material.Usually make by this long filament, film or sheet material and weave or supatex fabric.
The polyolefine that adopts the Ziegler-Natta type catalyst to make has a problem, promptly in the spinning of fiber and extruding in the operation of film, when melt extruding polyolefine, produces visible " cigarette ".Described " cigarette " results from the die head place, it is believed that it contains the volatile organic compounds that carbonatoms is 20-50.These volatile organic compoundss condensation subsequently that forms, and being coated on the equipment produces such problem, because volatile organic compounds is in die head place deposition, the feasible supatex fabric of being made by these fibers or film is inhomogeneous.
Known in polyolefine material and/or go up to add various additives and can improve thermostability, ultraviolet resistance and workability.For example, because residual little amount of catalyst in the polyolefine, so must in polyolefin compositions, add acid neutralizing agent.These residual catalysts can cause processing units for example die surface and die lip corrosion.Adding the appropriate amount of acid neutralizing agent just can avoid or reduce the corrosion that these residues cause at least.
But the selection of acid neutralizing agent is very important, because this can influence the total acidic/alkalescence of polyolefin compositions, and the reaction of the multiple organic additive in the impact polymer composition.In addition, acid neutralizing agent also can influence polyolefinic release property energy.
In fact, usually with Metallic stearates for example sodium salt, calcium salt and zinc salt add in the polyolefine material as acid neutralizing agent, wherein calcium stearate is the most frequently used.Though other acid neutralizing agent is known, based on calcium stearate, this is because it except being used as the acid neutralizing agent, can also play exterior lubricant and processing aid.
Usually in polyolefin compositions, add bi-ester of phosphite, comprise 2,2 ', 2 "-nitrilo [triethyl-three (3; 3 ', 5,5 '-tetra-tert-1,1-biphenyl-2; 2 '-two bases) phosphorous acid ester], make polyolefin compositions stable, with heat resistanceheat resistant degraded and oxidative degradation.Various forms of 2,2 ', 2 "-nitrilo [triethyl-three (3,3 ', 5,5 '-tetra-tert-1,1-biphenyl-2,2 '-two bases) phosphorous acid ester] is known.For example, in U.S. Patent No. 5,326, disclosed 2,2 ', 2 in 802 "-a kind of β crystal modification of nitrilo [triethyl-three (3,3 ', 5,5 '-tetra-tert-1,1-biphenyl-2,2 '-two bases) phosphorous acid ester].Embodiment 6 has disclosed the stable polypropylene that also contains calcium stearate.U.S. Patent No. 5,331,031 and 5,405,893 have disclosed 2,2 ', 2 "-a kind of γ crystal modification of nitrilo [triethyl-three (3,3 ', 5,5 '-tetra-tert-1,1-biphenyl-2,2 '-two bases) phosphorous acid ester].Embodiment 4 has illustrated the stable polypropylene that also contains calcium stearate.U.S. Patent No. 5,276,076 has disclosed 2,2 ', 2 "-a kind of amorphous solid metamorphosis of nitrilo [triethyl-three (3,3 ', 5,5 '-tetra-tert-1,1-biphenyl-2,2 '-two bases) phosphorous acid ester].Embodiment 3 has illustrated the stable polypropylene that also contains calcium stearate.
United States Patent (USP) № 5834541 has disclosed the polyolefin compositions that has low smoke generation, and it contains acid neutralizing agent and stabilising system except that the metal-salt of saturated or unsaturated fatty acids, and this stabilising system comprises specific phosphorous acid ester and N, N-dialkyl group azanol.Said composition is particularly suited for making fiber and film.
United States Patent (USP) № 5844029 has disclosed a kind of thermoplastic compounds, and it contains the amine oxide and the generalized auxiliary stabilizer of stable hydrocarbon.Do not illustrate that auxiliary stabilizer should be the acid neutralizing agent except that the metal-salt of saturated or unsaturated fatty acids.Embodiment has used the polypropylene that contains calcium stearate.
An object of the present invention is to provide a kind of polyolefin compositions, it produces minimum smog when extruding formation fiber or film.
Another object of the present invention provides the polyolefin compositions that has low smoke generation, its heat resistanceheat resistant degraded and oxidative degradation and stablize, and provide by its fiber that makes, film or fabric.
Another object of the present invention provides a kind of method, and it can reduce the volatile organic compounds that produces up to 90% when producing polyolein fiber, film or fabric.
The general introduction of invention
One aspect of the present invention relates to a kind of polymer composition, and it contains:
(i) contain the polyolefine of the acid neutralizing agent except that the metal-salt of saturated or unsaturated fatty acids,
(ii) be distributed in the stabiliser system in the whole polymkeric substance, it comprises:
(a) be selected from 2,2 ', 2 "-phosphorous acid ester of nitrilo [triethyl-three (3,3 ', 5,5 '-tetra-tert-1,1-biphenyl-2,2 '-two bases) phosphorous acid ester] and three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester; And
(b) stable hydrocarbon amine oxide.
Another aspect of the present invention relates to a kind of polymer composition, and it comprises:
(i) contain the polyolefine of the acid neutralizing agent except that the metal-salt of saturated or unsaturated fatty acids,
(ii) processing aid comprises the metal-salt of saturated or unsaturated fatty acids, and described content saturated or unsatuated metal salt is up to 200ppm,
(iii) be distributed in the stabiliser system in the whole polymkeric substance, it comprises:
(a) be selected from 2,2 ', 2 "-phosphorous acid ester of nitrilo [triethyl-three (3,3 ', 5,5 '-tetra-tert-1,1-biphenyl-2,2 '-two bases) phosphorous acid ester] and three (2,4-two-tert-butyl-phenyl) phosphorous acid ester; And
(b) stable hydrocarbon amine oxide.
One side more of the present invention relates to the method for preparing polyolein fiber or film, and it comprises:
(i) in the polyolefine that contains the acid neutralizing agent beyond the calcium stearate and/or go up and add stabiliser system, this stabiliser system comprises:
(a) be selected from 2,2 ', 2 "-phosphorous acid ester of nitrilo [triethyl-three (3,3 ', 5,5 '-tetra-tert-1,1-biphenyl-2,2 '-two bases) phosphorous acid ester] and three (2,4-two-tert-butyl-phenyl) phosphorous acid ester; And
(b) stable hydrocarbon amine oxide;
Make stable polyolefine thus; With
(ii) from die head, extrude stable polyolefine, make polyolein fiber, film or sheet material thus.
The detailed description of preferred implementation
The present inventor is surprised to find that, use the composition of (1) stable hydrocarbon amine oxide and specific phosphite ester stabilizer, with the controlled fused polyolefin of steady flow performance, (2) acid neutralizing agent beyond the metal-salt of saturated or unsaturated fatty acids just can significantly reduce the cigarette that produces in fiber, film and the sheet material course of processing.A specific embodiment of the present invention provides a kind of special polyolefin compositions meticulously, the metal-salt acid neutralizing agent in addition of saturated or unsaturated fatty acids is adopted in its (1), (2) contain the calcium stearate that the acid neutralizing agent effect is played in unusual few being not enough to, (3) contain and comprise the phosphorous acid ester selected and the stabiliser system of stable hydrocarbon amine oxide, to reduce the cigarette that produces owing to existing of calcium stearate.The composition that forms has the qualified processing characteristics that the polyolefine that contains the convention amount calcium stearate generally has, and the cigarette that produces when being extruded into fiber or film significantly is less than the polyolefin compositions that contains the convention amount calcium stearate.
The polyolefine of controlling flow sex change makes by following method: olefinic monomer is polymerized to higher weight-average molecular weight, uses peroxide treatment (" viscosity breaking ") so that its molecular weight is decreased to required mean value then.Also can use known ziegler-natta catalyst systems to prepare the controlled polyolefine of rheological property, so that required weight-average molecular weight to be provided, and the chain-transfer agent (as hydrogen) that during polyreaction, uses capacity, to obtain required melt flow rate (MFR).
Polyolefine obtains by at least a list-alpha-olefin of polymerization (as ethene, propylene, iso-butylene, butene-1,3-methyl-1-butene and 4-methyl-1-pentene).Polyethylene (homopolymer and multipolymer) can be middle density, high-density or LLDPE.
Also can use list-alpha-olefin copolymer in the composition of the present invention, as ethylene/propene copolymer, propene/but-1-ene-1 multipolymer, propylene/octene-1-multipolymer, ethylene/butylene-1 multipolymer, ethylene/octene-1 multipolymer and ethylene.
Also can use heterogeneous or impact-resistant modified polyolefine in the composition of the present invention.The phase polyolefin that is suitable for comprises:
(a) a kind of polyolefin compositions comprises:
(i) about 10-60 part (weight) crystalline polypropylene homopolymer, the isotactic index of described homopolymer be greater than 80, perhaps a kind of crystalline copolymer, and it is selected from (a) propylene and ethene, (b) propylene, ethene and C
4-C
8Alpha-olefin and (c) propylene and C
4-C
8Alpha-olefin, propylene content is greater than 85% (weight) in the described multipolymer, and isotactic index is greater than 85;
(ii) about 5 to 25 parts of (weight) ethene and propylene or C
4-C
8The multipolymer of alpha-olefin, it is insoluble to dimethylbenzene at ambient temperature; And
(iii) about 30 to 70 parts of (weight) elastomer copolymers, described multipolymer is selected from (a) ethene and propylene, (b) ethene, propylene and C
4-C
8Alpha-olefin, (c) ethene and C
4-C
8Alpha-olefin, described multipolymer randomly contain 0.5% (weight) of having an appointment to 10% (weight) diene, and contain and be less than 70% (weight) ethene, and are dissolved in dimethylbenzene at ambient temperature, and its limiting viscosity is about 1.5 to 4.0dl/g;
In the total amount of polyolefin compositions, component (ii) and total amount (iii) be about 50% to 90%, weight ratio (ii)/(iii) is less than 0.4, wherein said composition makes by two-stage polymerization reaction at least, its modulus in flexure is less than 150MPa;
(b) a kind of polyolefine comprises:
(i) about 10% to 60% (weight) homopolymer polypropylene, the isotactic index of described homopolymer be greater than 80, perhaps a kind of crystalline copolymer, and it is selected from (a) ethene and propylene, (b) ethene, propylene and C
4-C
8Alpha-olefin, (c) ethene and C
4-C
8Alpha-olefin, propylene content is greater than 85% (weight) in the described multipolymer, and isotactic index is greater than 85;
(ii) about 20% to 60% (weight) amorphous copolymer, described multipolymer is selected from (a) ethene and propylene, (b) ethene, propylene and C
4-C
8Alpha-olefin, (c) ethene and C
4-C
8Alpha-olefin randomly contains 0.5% (weight) of having an appointment to 10% (weight) diene in the described multipolymer, and contains and be less than 70% (weight) ethene, and is dissolved in dimethylbenzene at ambient temperature; And
(iii) about 3% to 40% (weight) ethene and propylene or C
4-C
8The multipolymer of alpha-olefin, it is insoluble to dimethylbenzene at ambient temperature;
The modulus in flexure of wherein said composition is preferably 200 to 1100MPa greater than 150MPa but less than 1200MPa, is preferably 200 to 1000MPa; And
(c) a kind of polyolefin compositions comprises:
(i) it is CH greater than 90 homopolymer polypropylene and isotactic index greater than 85 propylene and at least a formula that about 30% to 98% polymer materials, described polymer materials are selected from isotactic index
2The crystalline copolymer of the alpha-olefin of=CHR, R is H or C in the formula
2-C
6Alkyl, when R was H, the content of alpha-olefin was C less than 10% of multipolymer and work as R
2-C
6During the combination of alkyl or itself and R=H, its content is less than 20% of multipolymer, and
(ii) about 2% to 70% propylene and formula CH
2The elastomer copolymer of the alpha-olefin of=CHR, R is H or C in the formula
2-C
8During alkyl, the content of described alpha-olefin is about 45% to 75% of elastomer copolymer, and about 10% to 40% of elastomer copolymer is insoluble to dimethylbenzene at ambient temperature, perhaps ethene and C
4-C
8The elastomer copolymer of alpha-olefin, wherein the content of alpha-olefin is about 15% to 60%.
Be about 25 ℃ in this used room temperature or envrionment temperature.
The total amount of polymeric ethene preferably is about 10 to 40% (weight) in (a).
The preparation (a) and (b) in used C
4-C
8Alpha-olefin comprises for example butene-1, amylene-1, hexene-1,4-methyl-1-pentene and octene-1.
When having diene, it is generally divinyl, 1,4-hexadiene, 1,5-hexadiene or ethylidene norborneol material alkene.
Polyacrylic polymer material (a) and (b) can make by the reaction of two-stage polymerization at least, wherein in the first step polyreaction, polypropylene or propylene and ethene or alpha-olefin or propylene, ethene and alpha-olefin, generate (a) or component (b) (i), in next step polyreaction, polymerising ethylene and propylene or alpha-olefin, perhaps ethene, propylene and alpha-olefin, and the mixture of optional diene, generate (a) and component (b) (ii) and (iii).
(a) and polyreaction (b) can or use the liquid phase-gas phase of reactor separately carry out with liquid phase, gas phase, all these reactions can be intermittently to carry out or carry out continuously.For example, can use propylene liquid to carry out the polyreaction of component (i), carry out component (ii) and polyreaction (iii), except making the propylene partly degassed, not have other intermediate steps with gas phase as thinner.Preferable methods is whole gas-phase reactions.
At United States Patent (USP) 5,212, preparation amphoteric polymeric material (a) has been done more detailed narration in 246, this patent documentation is hereby incorporated by reference.At United States Patent (USP) 3,302, preparation amphoteric polymeric material (b) has been done more detailed narration in 454 and 5,409,992, these patent documentations are also incorporated by reference at this.
Polymer composition (c) can be in the presence of Ziegler-Natta catalyst, obtains by monomeric sequential polymerization reaction, perhaps by mechanical blending component (i) with (ii) obtain.Described sequential polymerization is reflected at United States Patent (USP) 5,486, more detailed narration is arranged in 419, and this patent documentation is hereby incorporated by reference.
Described sequential polymerization reaction also can be undertaken by following method: use the mixture of Ziegler-Natta catalyst and metallocene catalyst or use Ziegler-Natta catalyst in a reactor (being preferably first reactor), and use metallocene catalyst in other reactor (reactor after being preferably first reactor).
Can use the mixture of homopolymer or mixture or the two mixture of polyolefin copolymer.
Polyolefine is preferably crystaline polypropylene polymer, is preferably the crystalline polypropylene homopolymer of isotactic index greater than 90 (more preferably greater than 93), and perhaps isotactic index is greater than 85 propylene and ethene or C
4-C
10The crystallization of alpha-olefin, random copolymers.The preferred viscosity breaking of polypropylene to melt flow rate (MFR) (" MFR ") is 15-50g/10 minute, is preferably 25-38g/10 minute.This value is according to ASTM 1238, and Condition L measures.These propene polymers are available from Basell USA Inc. (f/k/a Montell USA Inc.).
The method of polyacrylic polymer material viscosity breaking is known by those skilled in the art.In general, carry out by the following method: with prodegradant or free-radical generating source (as liquid or Powdered superoxide) be sprayed on granular polyacrylic polymer (fine sheet that obtains as " polymerization " or through granulation) above or with its blend, perhaps be adsorbed on the carrier and/or in the carrier as polypropylene/superoxide masterbatch and its blend.Then, at elevated temperatures, propene polymer and superoxide or propene polymer/superoxide masterbatch are added the device (as extruding machine) that is used for thermoplastication or melt blending and this mixture of conveying.According to concrete selected superoxide (i.e. the transformation period of basis superoxide under the processing temperature of extruding machine), the control residence time and temperature are to reach the polymer chain degraded of required degree.Net result is to compare with former polymeric propene polymer, and the molecular weight distribution of propene polymer narrows down, and reduces total molecular weight, and increases MFR thus.For example, MFR is the propene polymer of mark (promptly less than 1), perhaps MFR be 0.5-10g/10 minute propene polymer can by the selectivity viscosity breaking to MFR be 15-50g/10 minute, be preferably 25-38g/10 minute, according to the type of selected superoxide, the temperature and the extruding machine residence time of extruding machine, need not undue experimentation.In actually operating, should give one's full attention to when the multipolymer that contains ethene exists, avoid taking place crosslinked; In general, when ethylene content in the multipolymer is enough low, can avoid crosslinked.
Polymer composition of the present invention also contains the outer acid neutralizing agent of metal-salt (especially Metallic stearates is specially calcium stearate) that removes saturated or unsaturated fatty acids.Lipid acid contains 4 to 22 carbon atoms usually, and has carboxyl (COOH) endways.Usually metal is Ia and the II family metal in periodictable.
In the acid that is suitable among the present invention and compound comprise the oxide compound and the oxyhydroxide of zeolite structured thing (hydrotalcite comprises natural and synthetical), pure aluminium silicate, lime carbonate, Sodium Benzoate and IA and IIA family metal.Most preferably calcium lactate, calcium hydroxide, calcium oxide or its mixture.If consider that wherein calcium stearate for the contribution of regulating calcium stearate content in the polyolefin compositions, then can use the hydrotalcite of the calcium stearate (in the weight of hydrotalcite) that contains 3-10 weight % usually.
According to the equivalent of polyolefinic acidity and acid neutralizing agent, the effective content of acid neutralizing agent be polymkeric substance 200 to 2000ppm, be preferably polymkeric substance 200 to 1000ppm.For polypropylene, the preferred content of acid neutralizing agent (as calcium lactate) be polymkeric substance 200 to 300ppm.
A specific embodiment of the present invention contains the metal-salt of few unusually saturated or unsaturated fatty acids, and its content is up to 200ppm.Preferred calcium stearate, content is preferably 100 to 200ppm, and more preferably 125 to 175ppm.
The applicant does not wish to be subjected to the constraint of any theory of the present invention.We think that acid neutralizing agent can work separately at present, can also work with unusual a spot of calcium stearate, with in and the acid that exists in the polymkeric substance.More particularly, the significant quantity of acid neutralizing agent depends on the amount of the calcium stearate processing aid that exists in the equivalent of selected specific acid neutralizing agent and the polymkeric substance.
Therefore, described calcium stearate can have dual-use function: (1) is as processing aid; (2) with acid neutralizing agent one be used from and polymer composition in contained acid.Importantly, during the content of calcium stearate itself is not enough to fully and the acid that exists in the polymer composition.
Phosphite ester stabilizer can be 2,2 ', 2 " nitrilo [triethyl-three (3,3 ', 5,5 '-tetra-tert-1,1-biphenyl-2,2 '-two bases) phosphorous acid ester] or three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester.These compounds all are on sale on the market.At United States Patent (USP) 4,318, disclosed 2,2 ', 2 in 845 "-preparation method of nitrilo [triethyl-three (3,3 ', 5,5 '-tetra-tert-1,1-biphenyl-2,2 '-two bases) phosphorous acid ester], the full text of this patent documentation is hereby incorporated by reference.
Amine oxide and manufacture method thereof be at the amine oxide of Richard J.Nadolsky, Encyclopedia ofChemical Technology, Vol2, page259-271, John Wiley ﹠amp; Sons Inc. has description in (1978), and the document is incorporated herein by reference.
Amine oxide preferably meets the saturated tertiary amine oxide of formula (I):
R wherein
1And R
2Each can choose wantonly naturally contain at least one-O-,-S-,-SO-,-CO
2-,-CO-or-the CON-partial C
6-C
36Residue; And
R
3Be also can choose wantonly and respectively contain at least one-O-,-S-,-SO-,-CO
2-,-CO-or-the CON-partial C
1-C
36Residue.
R
1, R
2And R
3Residue comprise the benzyl residue of benzyl and replacement.R
1, R
2And R
3It also can respectively be identical residue.R
1And R
2Preferred C
8-C
26Residue, most preferably C
10-C
26Residue, R
3Preferred C
1-C
22Residue, most preferable.Amine oxide also preferably includes wherein R
1, R
2And R
3Be identical C
6-C
36Residue.Preferred all above-mentioned R
1, R
2And R
3Residue all be the residue of stable hydrocarbon or contain above-mentioned at least one-O-,-S-,-SO-,-CO
2-,-CO-or-the stable hydrocarbon residue of CON-part.
Saturated amine oxide of the present invention also comprises poly-(amine oxide).Poly-(amine oxide) refers to that each intramolecularly contains the tertiary amine oxide of at least two tertiary amine oxides.The example of poly-(amine oxide) (being also referred to as " poly-(tertiary amine oxide) ") comprises the analogue of the tertiary amine oxide of following diamines, i.e. fat and alicyclic diamine for example 1,4-diaminobutane, 1,6-diamino hexane, 1,10-diamino decane, 1,4-diamino-cyclohexane and aromatic base diamines, for example diamino-anthraquinone and diamino anisole.Also comprise by the oligopolymer of above-mentioned diamines and the tertiary amine oxide of polymer formation.Useful amine oxide also comprises the amine oxide that is connected with following polymkeric substance, for example polyolefine, polyacrylic ester, polyester, polymeric amide, polystyrene etc.When amine oxide was connected with polymkeric substance, the average number of amine oxide can alter a great deal in each polymer chain, and not every polymer chain all needs to contain amine oxide.Usually, the number of amine oxide part is about 0.001-5% (weight) in useful total thermoplastic resin, is benchmark with the thermoplastic compounds gross weight.Above-mentioned all amine oxides can choose wantonly contain at least one-O-,-S-,-SO-,-CO
2-,-CO-or-the CON-part.In a preferred implementation, each tertiary amine oxide of polyoxygenated tertiary amine all contains C
1Residue.
In a preferred embodiment of the present invention, saturated amine oxide is connected with the molecule that contains hindered amine.Hindered amine is known in the industry, and amine oxide of the present invention can be connected with hindered amine with the structure position of hindered amine in any way.Useful hindered amine comprises general formula (II) and hindered amine (III) among the present invention.
Wherein K is the carbochain that contains amine oxide (one or more amine oxide).
Y is C
1-30Moieties, wherein R is C
1-30Alkyl-C (O) R part or wherein R be C
1-30Alkyl-the OR part, each R
4Each is C naturally
1-30Alkyl, preferable methyl.Comprise also that each intramolecularly contains an above hindered amine and the amine oxide of saturated amine oxide more than.Hindered amine can be connected with poly-(tertiary amine oxide), or is connected with polymeric substrate, as mentioned above.
The present invention also comprises the thermal response product of tertiary amine oxide.At high temperature, for example be used for preparing the material of thermoplastic compounds of the present invention, it is believed that the amine oxide of the amine oxide that comprises that formula I represents can experience the various reactions that generate azanol and olefinic substances that it is believed that.In order to improve the solubleness of reaction product in thermoplastic resin, preferably contain the amine oxide reaction product of at least one long-chain carbon residue, comprise the reaction product of azanol type.Only an alkyl substituent (is R in tertiary amine oxide
1, R
2And R
3In only one) be C
6-C
36Residue, and other two alkyl substituents are C
1-5During residue, it (is C that the reaction product that it is believed that part azanol type only contains the short chain substituting group
1-5Residue).It is believed that this is that part long-chain residue removes the result who forms the olefinic by product from amine oxide.In order to guarantee that at least one long-chain is retained in the thermal response product of azanol type, preferably long-chain or a chain can be C to three substituting groups entirely
1(for example methyl), and other two substituting groups are long-chain (C for example
6-C
36Residue).When a substituting group is C
1Residue, other two substituting groups are long-chain residues when (comprising above-mentioned polymer residue), and the thermal response product of formation will be asymmetric, and contain C
1Residue and long-chain residue.Long-chain carbon residue refers to C
6To about C
36, preferred C
8-C
26, C most preferably
10-C
22The long-chain residue also comprises above-mentioned polyoxygenated amine residue.Long-chain carbon residue also can be chosen wantonly and contain at least one above-mentioned R
1, R
2And R
3-O-,-S-,-SO-,-CO
2-,-CO-or-the CON-part.The azanol type reaction product that does not contain above-mentioned long-chain residue can move from thermoplastic resin, can make thermoplastic resin surface frosting, or covers the surface of processing units, needs to stop work and clears up and keep in repair, and this is very expensive.Can understand from above-mentioned explanation, the present invention includes the amine oxide that contains at least one long-chain carbon residue, preferably contain the asymmetric oxidation amine of long-chain and short chain; Comprise that also each intramolecularly contains the polyoxygenated amine of at least two amine oxides.
Be used for preferred saturated amine oxide of the present invention and comprise dioctyl methyl oxidation amine, trioctylphosphine amine oxide, didecyl methyl oxidation amine, three decyl amine oxides, two (cocounut oil alkyl) methyl oxidation amine, three (cocounut oil alkyl) amine oxides, two (tallow alkyl) methyl oxidation amine, three (tallow alkyl) amine oxide, three (C
20-C
22) amine oxide and two (C
20-C
22Alkyl) methyl oxidation amine.Preferred saturated azanol comprises octyl group methyl hydroxylamine, decyl methyl hydroxylamine, (cocounut oil alkyl) methyl hydroxylamine, (tallow alkyl) methyl hydroxylamine and (C
20-C
22Alkyl) methyl hydroxylamine." cocounut oil alkyl " speech refers to hydrogenation C
12-C
14Alkyl is commonly referred to hydrogenated coconut oil." tallow alkyl " speech refers to hydrogenation C
16-C
18Alkyl is commonly referred to the hydrogen tallow oil.Hydrogenated tallow oil has description in United States Patent (USP) № 4876300.Above-mentioned hydrogenated coconut oil and hydrogenated tallow oil contain above-mentioned length of part percentage and/or short carbochain, should be understood that these other parts within the scope of the invention.Preferably at least 75% carbochain is in the scope of above-mentioned Oleum Cocois and tallow oil.
The effective content of stabiliser system is generally the 250-2000ppm of polymkeric substance, be preferably polymkeric substance 700 to 1500ppm.Stabiliser system can contain 5-80% (weight) stable hydrocarbon amine oxide and 95-20% phosphorous acid ester, preferred 5-45% and 95-55%, most preferably 5-25% and 95-75% (weight).
Stabiliser system of the present invention also can contain at least a other stabilizer compounds.For example, for the purpose that reduces cost, can use another kind of bi-ester of phosphite partly to substitute main phosphite ester stabilizer compound.Yet the present inventor finds that this substitutes can only be that part substitutes (promptly about 50%); Substitute the cigarette showed increased that main bi-ester of phosphite will make generation fully.Be applicable to that part alternate phosphorous acid ester comprises three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester and 2,4,6-tri-tert phenyl-2-butyl-2-ethyl-1, ammediol phosphorous acid ester.
Stabiliser system also can comprise and commonly used has little or no the stabilizer compounds of disadvantageous effect to giving birth to cigarette.For example, hindered amine as light stabilizer (HALS) can be added in the stabiliser system.That the HALS that is suitable for comprises is poly-[6-[(1,1,3,3-tetramethyl--butyl) amino-s-triazine-2, the 4-yl] (2,2,6,6-tetramethyl--4-piperidyl) imino-] hexa-methylene [(2,2,6,6-tetramethyl--4-piperidyl) imino-] and 1,3,5-triazines-2,4,6-triamine-N; N "-[ethylene (ethanedyl) two [N-(3-[4,6-two (butyl-1,2,2,6,6-pentamethyl--4-piperidyl) amine] propyl group-[N-two (1 for N, N-dibutyl-N, 2,2,6,6-pentamethyl--4-piperidyl).Equally, (as octadecyl-3,5-di-t-butyl-4-hydroxyl hydrogenated cinnamate and four [methylene radical-3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic ester] methane is to improve thermostability also can to add phenol stabilizer.
Stable polyolefin compositions can contain other suitable additive according to the intended purpose of said composition.These additives comprise static inhibitor, fire retardant, anti, lubricant, pigment, white dyes, nucleator and transparent base.
Each component of stabiliser system can with the method for any routine (as with rotary drum mixer and Henschel blending machine with stabiliser system directly with the polymeric aggregate dry blending) in the adding polyolefine.Solution, emulsion or the slurry of stabiliser system can be sprayed on the polymer beads or with it and mix.For example, can be according to U.S. Patent No. 5,141,772 method is coated in each stabilizer component on the polyolefin particles in fluidized-bed, and the full text of above-mentioned patent documentation is hereby incorporated by reference.Also available Banbury, Bradbender mixing machine, roller refining machine or screw extruder are with each stabilizer component and fused polymer blending.
This stabiliser system also can be according to U.S. Patent No. 5,236, and the routine techniques described in 962 adds in the polyolefine with master batch form, and the full text of above-mentioned patent documentation is hereby incorporated by reference.
Stable polyolefin compositions of the present invention is particularly suitable for making fiber or film with routine techniques and device.More particularly, stable polyolefine can be extruded by die head at conventional temperature (promptly 210 to 280 ℃), quenching, partly or entirely the orientation and be rolled onto on the bobbin before heat setting type, or further be processed into spunbond or meltblown fibers, and finally become and weave and supatex fabric.
Term used herein " supatex fabric " is meant the fabric with ultimate fibre or yarn shop interposed structure, but the mode that put the shop is different with knit goods.Supatex fabric can be formed by several different methods, becomes net method (bonded carded web process) as meltblown, spun-bond process and bonded carded.With ounce number (osy) or every square Mick number (gsm) expression of every square yard material, usually with micron represent usually by Fibre diameter for the unit weight of supatex fabric.
Term used herein " spun-bonded fibre " is meant the fiber of minor diameter, and these fibers are by molten thermoplastic material being extruded from a plurality of orifices with normally circular fine, soft fur tubule shape of the diameter of extruding long filament, being formed long filament, subsequently as for example United States Patent (USP) 4,340,563,3,692,618,3,802,817,3,338,992,3,341,394,3,502,763 and 3,542,615 described modes reduce diameter fast and make.It is generally inviscid when spun-bonded fibre is deposited on the collection surface.Spun-bonded fibre generally is a successive, and mean diameter (being obtained by at least 10 sample means) more specifically, is about the 10-20 micron greater than 7 microns.
In this article, term " meltblown fibers " refers to the fiber that made by following method: molten thermoplastic material is extruded from a plurality of normally circular die head fine, soft fur tubules, form molten state fine rule or long filament, converge with normally hot high velocity air (as air), this air-flow attenuates to reduce its diameter molten state thermoplastic material long filament, and this diameter can be reduced to the diameter of primitive fiber.This meltblown fibers of high velocity air carrier band and it is deposited on the collection surface forms the meltblown fibers fabric of random dispersion subsequently.This method can be referring to United States Patent (USP) 3,849,241.Meltblown fibers can be continuous or discontinuous primitive fiber, and mean diameter is generally less than 10 microns, generally has viscosity when being deposited on the collection surface.United States Patent (USP) 5,667,562 disclose and adopt spun-bond process to make the method for filtration medium with the polypropylene-base fiber, and the document is drawn at this and to be reference.
Particularly preferred polypropylene resin composite contains 800ppm2,2 ', 2 "-nitrilo triethyl-three (3,3 ', 5,5 '-tetra-tert-1,1-biphenyl-2,2 '-two bases) phosphorous acid ester, 500ppm methyl (two-C
14-22) amine oxide, 500ppm four [methylene radical (3,5-di-t-butyl-4-hydroxyl hydrogenated cinnamate)] methane and 250ppm be as the calcium lactate of acid neutralizing agent.
Embodiment
These embodiment just are used for explanation, and should not think any restriction to character of the present invention and scope.
The compound trade mark and the title of used product are as follows in following prescription:
Phosphorous acid ester
Irgafos 12 2, and 2 ', 2 "-nitrilo [triethyl-three (3,3 ', 5,5 '-tetra-tert-1,1-biphenyl-2,2 '-two bases) phosphorous acid ester]: available from Ciba Specialty Chemicals Corporation.
Amine oxide
Genox EP N, N-two (C
14-22) amine oxide, available from General Electric SpecialtyChemicals.
Other
Pationic 1240 calcium lactates: available from American Ingredients Company.
Lupersol 101 2,5-dimethyl-2, and 5-two-(t-butyl peroxy) hexane is available from Elf AtochemNorth America, Inc..
Except as otherwise noted, all consumptions herein all refer to umber (weight).
Embodiment 1
The pp material that is made by industrial crystalline p p sheet prepares three kinds of sample recipe ingredients, its at room temperature in the dimethylbenzene solvable amount be 4.0%, initial MFR is 1.5g/10 minute, according to ASTM 1238, ConditionL records, and viscosity breaking was to target MFR 35g/10 minute.
Recipe ingredient with these samples together mixes then, and extruding pelletization.Estimate cigarette and yellowness index that every kind of prescription sample produces.
Extrude 10 pounds of samples of respectively filling a prescription with 10 Pounds Per Hours speed, measure the cigarette that produces.Measure volatile organic compounds and record with following method: will be released into the sample chamber by the smog of vacuum system from the sucking-off of die head aperture, and measure the concentration of volatile particles by laser particle counter in this sample chamber, unit is every cubic metre of milligram.
According to ASTM-D 1925-70, the I part adopts Hunter D25P-2 calorimeter with total transmission mode, and the test color is at first calibrated as benchmark with air.Huang Du is defined as departing from whiteness in the 570-580nm dominant wavelength ranges.Yellowness index (YI) is the tolerance with respect to the yellow value degree of magnesium oxide marker.This value is more little, and color is good more.
Table 1
| Component | ????I-1 | ????I-2 | ????I-3 |
| Polypropylene | ????100 | ????100 | ????100 |
| GENOX EP amine oxide | ?????- | ????0.04 | ????0.04 |
| Calcium stearate | ????0.05 | ?????- | ?????- |
| Irgafos 12 phosphorous acid esters | ?????- | ?????- | ????0.08 |
| Pationic 1240 lactic acid salts | ?????- | ????0.025 | ????0.025 |
| Lupersol 101 superoxide | ????** | ????** | ????** |
| ????MFR，g/10min | ????64.1 | ????41.9 | ????40.1 |
| Cigarette, mg/m 3 | ????240 | ????180 | ????9.5 |
| Yellowness index | ????-0.47 | ????-0.18 | ????-0.58 |
The test result explanation of table 1, the combination of amine oxide and phosphite ester stabilizer can significantly reduce the formation of volatile organic compounds.More particularly, the control sample I-1 that does not contain stablizer with containing convention amount calcium stearate (550ppm), with contain amine oxide do not contain phosphite ester stabilizer with non-calcium stearate acid scavenger control sample I-2 and compare, the volatile organic compounds that sample I-3 of the present invention produces significantly reduces.
After its its feature of the present invention, advantage and the embodiment of this announcement have been read above for the person of ordinary skill of the art will be conspicuous.Therefore, though quite be described in detail specific embodiments more of the present invention in the literary composition, in not departing from the claimed spirit and scope of the present invention, can carry out changes and improvements to these embodiments.
Claims (21)
1. polymer composition, it comprises:
(i) contain the polyolefine of the acid neutralizing agent except the metal-salt of saturated or unsaturated fatty acids,
(ii) be distributed in the stabiliser system in the whole described polymkeric substance, described stabiliser system comprises:
(a) be selected from 2,2 ', 2 "-phosphorous acid ester of nitrilo [triethyl-three (3,3 ', 5,5 '-tetra-tert-1,1-biphenyl-2,2 '-two bases) phosphorous acid ester] and three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester; And
(b) stable hydrocarbon amine oxide.
2. polymer composition as claimed in claim 1, wherein said acid neutralizing agent are to be selected from least a in the oxide compound of hydrotalcite, pure aluminium silicate and II family metal and the oxyhydroxide.
3. polymer composition as claimed in claim 2, wherein said acid neutralizing agent is selected from calcium lactate, calcium hydroxide, calcium oxide and composition thereof.
4. polymer composition as claimed in claim 1, wherein said phosphorous acid ester are 2,2 ', 2 "-nitrilo [triethyl-three (3,3 ', 5,5 '-tetra-tert-1,1-biphenyl-2,2 '-two bases) phosphorous acid ester].
5. polymer composition as claimed in claim 1, wherein said amine oxide meet formula (I):
R wherein
1, R
2And R
3Respectively be selected from alkyl, aryl, aralkyl, alkaryl, cycloalkyl, alkane cycloalkyl and alkyl naphthene, respectively have 1-36 carbon atom in each group, condition is, if R
1, R
2And R
3In one be the alkyl that has 6-36 carbon atom in each group, R so
1, R
2And R
3In in addition two just can not be the alkyl that has 1-5 carbon atom in each group simultaneously.
6. polymer composition as claimed in claim 5, wherein said hydrocarbon amine oxide is a trialkylamine oxides.
7. polymer composition as claimed in claim 5, wherein said amine oxide are three (C
12-C
22) amine oxide.
8. polymer composition as claimed in claim 5, the significant quantity amine oxide of wherein said stabilising thermoplastic resin is and the thermoplastic resin blended.
9. polymer composition as claimed in claim 1, the content of wherein said stabiliser system be polymkeric substance 250 to 2000ppm.
10. polymer composition as claimed in claim 9, the content of wherein said stabiliser system are the 700-1500ppm of polymkeric substance.
11. polymer composition as claimed in claim 1, wherein said stabiliser system contain 10-80% stable hydrocarbon amine oxide and 90-20% phosphorous acid ester.
12. polymer composition as claimed in claim 1, it also contains:
(c) at least a other stabilizer compounds, described other stablizer comprises and is selected from phenol, hindered amine and removes 2,2 '; 2 "-nitrilo [triethyl-three (3,3 ', 5,5 '-tetra-tert-1,1-biphenyl-2,2 '-two bases) phosphorous acid ester] or three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester beyond phosphorous acid ester at least a.
13. polymer composition as claimed in claim 1, wherein said polyolefine are isotactic indexs greater than 90 crystalline polypropylene homopolymer, or propylene and ethene or C
4-C
10The crystallization of alpha-olefin, random copolymers.
14. polymer composition as claimed in claim 1, it also comprises the processing aid of the metal-salt that contains saturated or unsaturated fatty acids, and the high-content of the metal-salt of saturated or unsaturated acid is 200ppm.
15. polymer composition as claimed in claim 14, wherein said processing aid contains the calcium stearate of 100-200ppm.
16. polymer composition as claimed in claim 15, the content of wherein said calcium stearate are 125-175ppm.
17. a method for preparing polyolein fiber or film, it comprises
(i) the stabiliser system adding is contained in the polyolefine of the acid neutralizing agent except the metal-salt of saturated or unsaturated fatty acids, described stabiliser system comprises:
(a) be selected from 2,2 ', 2 "-phosphorous acid ester of nitrilo [triethyl-three (3,3 ', 5,5 '-tetra-tert-1,1-biphenyl-2,2 '-two bases) phosphorous acid ester] and three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester; And
(b) stable hydrocarbon amine oxide is made stable polyolefine thus; And
(ii) this stable polyolefine is extruded from die head, made polyolein fiber or film thus.
18. the fiber that method according to claim 17 makes.
19. the film that method according to claim 17 makes.
20. comprise the fabric of many fibers as claimed in claim 18.
21. fabric as claimed in claim 20, wherein said fabric are the supatex fabric that makes with spun-bond process or meltblown.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US46585199A | 1999-12-17 | 1999-12-17 | |
| US09/465,851 | 1999-12-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1344289A true CN1344289A (en) | 2002-04-10 |
Family
ID=23849428
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00805156A Pending CN1344289A (en) | 1999-12-17 | 2000-12-08 | Olefin polymer compsn. having low smoke generation and fiber, film and fabric prepared therefrom |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP1153073A1 (en) |
| JP (1) | JP2003517077A (en) |
| KR (1) | KR20010102249A (en) |
| CN (1) | CN1344289A (en) |
| AR (1) | AR026998A1 (en) |
| AU (1) | AU1545101A (en) |
| BR (1) | BR0008327A (en) |
| CA (1) | CA2368286A1 (en) |
| WO (1) | WO2001044362A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111788267A (en) * | 2018-02-02 | 2020-10-16 | 格雷斯公司 | Antacids for polymers |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200422333A (en) * | 2002-09-30 | 2004-11-01 | Sunoco Inc R&M | Polyolefin compositions exhibiting enhanced stain resistance |
| US20040147650A1 (en) * | 2003-01-24 | 2004-07-29 | General Electric Company | Process for stabilization of polymer compositions |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5844029A (en) * | 1995-09-25 | 1998-12-01 | General Electric Company | Polymer compositions containing hydrocarbon amine oxide and hydrocarbon amine oxide stabilizer compositions |
| US5922794A (en) * | 1997-03-26 | 1999-07-13 | General Electric Company | Compositions stabilized with tertiary amine oxides |
| US5834541A (en) * | 1997-05-02 | 1998-11-10 | Montell North America Inc. | Olefin polymer composition having low smoke generation and fiber and film prepared therefrom |
-
2000
- 2000-12-08 JP JP2001544844A patent/JP2003517077A/en active Pending
- 2000-12-08 AU AU15451/01A patent/AU1545101A/en not_active Abandoned
- 2000-12-08 CN CN00805156A patent/CN1344289A/en active Pending
- 2000-12-08 EP EP00977820A patent/EP1153073A1/en not_active Ceased
- 2000-12-08 CA CA002368286A patent/CA2368286A1/en not_active Abandoned
- 2000-12-08 BR BR0008327-5A patent/BR0008327A/en not_active Application Discontinuation
- 2000-12-08 WO PCT/IB2000/001830 patent/WO2001044362A1/en not_active Application Discontinuation
- 2000-12-08 KR KR1020017010506A patent/KR20010102249A/en not_active Application Discontinuation
- 2000-12-18 AR ARP000106724A patent/AR026998A1/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111788267A (en) * | 2018-02-02 | 2020-10-16 | 格雷斯公司 | Antacids for polymers |
| US11643481B2 (en) | 2018-02-02 | 2023-05-09 | W.R. Grace & Co.-Conn. | Antacids for polymers |
Also Published As
| Publication number | Publication date |
|---|---|
| AR026998A1 (en) | 2003-03-12 |
| AU1545101A (en) | 2001-06-25 |
| BR0008327A (en) | 2002-01-22 |
| EP1153073A1 (en) | 2001-11-14 |
| KR20010102249A (en) | 2001-11-15 |
| WO2001044362A1 (en) | 2001-06-21 |
| JP2003517077A (en) | 2003-05-20 |
| CA2368286A1 (en) | 2001-06-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1198448A (en) | Less smoke generated olefine polymer composition and the fibre and film made from it | |
| US6448334B1 (en) | Translucent polycarbonate composition, method for preparation thereof, and articles derived therefrom | |
| KR101008786B1 (en) | Plasticized polyolefin compositions | |
| CN1068356C (en) | Linear low density polyethylene based compositions with improved optics | |
| US20060247332A1 (en) | Method to make an article comprising polymer concentrate | |
| CN1122069C (en) | Syndiotactic polypropene composition, processing method and product made therefrom | |
| US20110105667A1 (en) | Polyolefin composition | |
| CN1336945A (en) | Synthetic polymers comprising additive blends with enhanced effect | |
| CN1143656A (en) | Polyolefin compositions resistant to high energy radiation, and articles produced therefrom | |
| WO2007050393A2 (en) | Thermoplastic blend compositions as soft coupling agents | |
| CN1272863A (en) | Olefin polymer composition having low smoke generation and fiber, film and fabric prepared therefrom | |
| AU2003220501A1 (en) | Extrudable thermoplastic compositions | |
| US6444736B1 (en) | Flame retardant polyolefin composition | |
| CN1344289A (en) | Olefin polymer compsn. having low smoke generation and fiber, film and fabric prepared therefrom | |
| CN1068019C (en) | Antiblocking agent master batch and oriented polyolefin resin film using the same | |
| CN112739767B (en) | Flame retardant polypropylene composition | |
| CN1761711A (en) | Irradiated, oxidized olefin polymer dispersing agents | |
| EP0721969B1 (en) | Syndiotactic polypropylene resin composition | |
| JP5745318B2 (en) | Polyolefin resin composition containing a high amount of inorganic filler, and inflation film comprising the same | |
| JP4171676B2 (en) | Polyolefin resin composition | |
| MXPA00001064A (en) | Olefin polymer composition having low smoke generation and fiber, film and fabric prepared therefrom | |
| MXPA98003375A (en) | Composition of polymers of olefins that produce smoke, and fiber and film prepared as a whole |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |