WO2001010914A1 - Azidosilane-modified, moisture-curable polyolefin polymers, process for making, and articles obtained therefrom - Google Patents
Azidosilane-modified, moisture-curable polyolefin polymers, process for making, and articles obtained therefrom Download PDFInfo
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- WO2001010914A1 WO2001010914A1 PCT/US2000/020912 US0020912W WO0110914A1 WO 2001010914 A1 WO2001010914 A1 WO 2001010914A1 US 0020912 W US0020912 W US 0020912W WO 0110914 A1 WO0110914 A1 WO 0110914A1
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- polymer
- silane
- ethylene
- grafted
- azidosilane
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
Definitions
- This invention relates to silane-grafted polyolefin polymers, more specifically to
- silane-grafted homogeneous ethylene polymers HEP
- This invention also relates to a process of making the moisture-
- curable azidosilane-grafted polymers compositions made from the polymers, and articles
- the invention also relates to processes for making the
- Silane-grafted polymers are frequently used in applications requiring good
- silane-grafted polymers Prior to being exposed to moisture, silane-grafted polymers are
- Silane-grafting can also be used to improve adhesion/compatibility between
- polyolefins and polar substrates like glass, aluminum or polyesters.
- grafting refers to insertion of one of the nitrogens from
- a "grafting agent” is an azidosilane that is capable of reacting with a polymer
- Silane modification of a polyolefin is usually achieved via peroxide grafting of
- VTMOS vinyltrimethoxysilane
- gelling is due to the polymer chains forming radicals that can crosslink with other
- An inte ⁇ olymer is a polymer produced from at least two different monomers.
- interpolymers include, inter alia, copolymers (two monomers) and terpolymers
- crosslinking refers to forming a bridge between two or
- crosslinking is formed by primary bonds between an atom or molecule (the "crosslinking
- Crosslinking thus differs from grafting
- crosslinking requires that the crosslinking agent have multiple sites that can react
- the grafting agent can have only one such site.
- MWD Molecular weight distribution
- weight average molecular weight (M w ) to number average molecular weight (M n ) i.e.
- MJM n can be measured directly, e.g., by gel permeation chromatography techniques, or
- LLDPE linear low density polyethylene polymers
- linear high density polyethylene polymers typically are made using Ziegler Natta
- LDPE low density polyethylene
- HDPE high density polyethylene
- the polymer has several different types of branching within the same polymer
- heterogeneous polymers produced in the Ziegler Natta process also have broad molecular
- homogeneous polymers refers to polymers made using uniform
- homogeneous polymers include those linear homogeneous polymers made as described in
- the uniformly branched/homogeneous polymers are those
- polymers have an absence of long chain branching, as, for example, Exxon Chemical has
- SCBDI Short Chain Branch Distribution Index
- CDBI Composition
- Distribution Branch Index is defined as the weight percent of the polymer molecules
- TREF TREF
- CDBI for the homogeneously branched linear or homogeneously branched substantially
- linear olefin polymers of the present invention is greater than 50 percent, preferably greater
- Homogeneous polymers have a homogeneous branching distribution and typically
- substantially linear means that the polymer has long chain branching
- branches/1000 carbons to 1 long chain branches/1000 carbons, and especially from 0.05
- ethylene polymer means a homopolymer made from a
- substantially linear ethylene polymers is, of course, at least one carbon longer than
- the long chain branch in an ethylene/1-octene substantially linear polymer, the long chain branch
- branch has to be longer than the side chain resulting from incorporation of comonomer.
- the long chain branch is also
- low density refers to polymers with a density no more than 0.900
- the invention includes an azidosilane grafted polymer of formula (I):
- (A) M is a polymer repeating unit in a polymer selected from the group
- (B) a is the number of polymer units in the polymer chain
- (C) G is selected from the group consisting of a sulfonyl group and a carbonyl
- (D) R is selected from the group consisting of hydrocarbon or inertly-
- (E) Z is, independently each occurrence, a hydrogen, an organic radical, a
- hydrolyzable group (including, inter alia, alkoxy groups) or a halogen
- (F) b is the number of silane molecules grafted onto the polymer chain
- hydrocarbon is an organic compound consisting exclusively of the elements
- alkenes alkadienes, acetylenes, and acyclic terpenes
- cyclic alicyclic, aromatic
- the invention includes a water-curable, silane-grafted polymer comprising the
- a "polymer unit” is the portion of a polymer formed from a single monomer or
- the invention further includes a process for producing a water-curable silane-
- azidosilane the azidosilane having a decomposition temperature
- silane-grafted polymer
- decomposition temperature of the azide it is meant that temperature at which the azide
- the invention also includes the water curable silane-grafted polymers produced by
- silane-grafted polymer The invention also includes the use of a composition of the invention in any of
- ⁇ -olefin C 3 to C 20
- EPDM ethylene copolymers with unsaturation
- high density polyethylene substantially random inte ⁇ olymers of at least one ⁇ -olefin
- ethylene-styrene inte ⁇ olymers including ethylene-styrene inte ⁇ olymers, syndiotactic polystyrene, atactic polystyrene,
- the polymers are advantageously prepared using single site
- ⁇ -olefin is used to refer to any of a class of unsaturated open-chained
- hydrocarbons having the general formula R'j n , where R 1 is a hydrogen, alkyl, other
- n is the number of carbon atoms in the chain
- double bond is located between the first and second carbon atoms from an end of the
- n is any integer greater than 2.
- Inert substituents are atoms or groups that are not reactive with each other, other polymer
- vinylidene aromatic or "vinylaromatic” refers to a phenyl radical
- Preferred polymers for use in the practice of the invention are polymers prepared
- Such monomers include ⁇ -olefins and other monomers having
- the polymer is a polyolefin, optionally a homopolymer,
- copolymer or other inte ⁇ olymer.
- homo- or copolymers contain ethylene
- polyethylene copolymers the comonomer content is preferably greater
- ethylene preferably an ⁇ -olefin or cyclic olefin, more preferably such an olefin of less
- content is at least one comonomer polymerizable with ethylene, preferably less than 4
- comonomers polymerizable with ethylene, more preferably less than 2 such comonomers.
- the ethylene polymers are optionally any inte ⁇ olymers of ethylene and at least
- ⁇ -olefins are represented by formula (II):
- R 2 is a hydrocarbyl radical.
- R 2 generally has from one to twenty carbon atoms.
- Suitable ⁇ -olefins for use as comonomers include 1-propylene, 1-butene, 1 -isobutylene,
- olefin will be 1-butene, 1-pentene, 4-methyl-l-pentene, 1-hexene, 1-heptene, 1-octene, or
- the ⁇ -olefin will be 1-hexene, 1-heptene, 1-octene, or mixtures thereof. Most preferably, the ⁇ -olefin is 1-octene.
- silane-grafted according to this invention is more preferably a SLEP (defined
- inte ⁇ olymers preferably contain at least 2 weight percent, more
- preferred embodiment include a third monomer having at least two double bonds
- Suitable diene and triene comonomers include 7-methyl-l,6-
- 1,6,10-octatriene 6-methyl-l,5-heptadiene, 1,3-butadiene, 1 ,6-heptadiene, 1 ,7-octadiene,
- hexadienes and octadienes, most preferably 1 ,4-hexadiene, 4-methyl-l,4-hexadiene, 5-
- inte ⁇ olymers of this invention may include other monomers, such as vinyl
- benzocyclobutane and cycloalkadienes e.g., cyclopentadiene, cyclohexadiene,
- Polyolefms are formed by means within the skill in the art.
- the density of the HEP as measured in accordance with ASTM D-792 is generally
- I 2 of the homogeneous ethylene polymer is generally from 0.01 g/10 min. up
- the molecular weight distributions of the polymers are determined by gel
- the solvent is 1 ,2,4-trichlorobenzene, from which 0.3
- milliliters/minute, unit operating temperature is 140°C and the injection size is 100
- polyethylene molecular weights are determined by using appropriate Mark-Houwink
- M po lyethylene a * (M po lystyrene) b -
- the homogeneous ethylene polymer has M /M n less than or equal to 3.3, preferably
- starting material polyolefins are preferably substantially
- EG 8100, and CL 8001 and specific examples of useful AFFINITYTM POPs include FM-
- SLEPs can be prepared via the solution, slurry, or gas
- phase preferably solution phase, polymerization of ethylene and one or more optional
- ⁇ -olefin comonomers in the presence of a constrained geometry catalyst, such as the
- gas extrusion rheometry of greater than 4 x 10 6 dynes/cm 2 or a gas extrusion rheology such that the critical shear rate at onset of surface melt
- linear ethylene polymer has an I 2 , MJM n and preferably density which are
- Suitable ethylene or ⁇ -olefin monomers include, for example, those ⁇ -olefin
- Preferred such monomers include ethylene, propylene, butene-1 , 4-
- strained ring olefms such as norbornene and C,. ]0 alkyl or C 6 . ]0 aryl substituted
- norbornenes with an exemplary inte ⁇ olymer being ethylene/styrene/norbornene.
- inte ⁇ olymers employed in the invention include, for example, those represented by the
- R 3 is selected from the group of radicals consisting of hydrogen and alkyl
- Ar is a radical containing from 1 to 4 carbon atoms, preferably hydrogen or methyl;
- phenyl group or an inertly-substituted phenyl group e.g., a phenyl group substituted with
- reagents under polymerization conditions include such groups as halo, C -alkyl,
- n has a value from zero to 6, preferably from zero to 2, most
- Exemplary vinyl aromatic monomers include styrene, vinyl toluene, ⁇ -
- Particularly suitable such monomers include styrene and lower alkyl- or
- Preferred monomers include styrene, ⁇ -methyl
- styrene the lower alkyl- (C, - C 4 ) or phenyl-ring substituted derivatives of styrene, such
- a R 3 _ C C(R 4 ) 2
- a 1 is a sterically bulky, aliphatic or cycloaliphatic substituent of from 3 up to 20
- R 3 is selected from the group of radicals consisting of hydrogen and alkyl
- R 3 and A 1 together form a ring system.
- monomers are those in which one of the carbon atoms bearing ethylenic unsaturation is
- substituents include cyclic aliphatic
- norbornene Especially suitable are 1-, 3-, and 4-vinylcyclohexene.
- monomers employed in the present invention are substantially random polymers.
- inte ⁇ olymers usually contain from 0.5 to 65, preferably from 1 to 55, more preferably
- aliphatic or cycloaliphatic vinyl monomer and from 35 to 99.5, preferably from 45 to 99,
- strained ring olefms such as norbornene and C,., 0 alkyl or C 6 . 10 aryl substituted
- norbornenes with an exemplary inte ⁇ olymer being ethylene/styrene/norbornene.
- the number average molecular weight (Mn) of the polymers and inte ⁇ olymers is
- atactic vinyl aromatic homopolymer may be formed due to
- the vinyl aromatic homopolymer may be any vinyl aromatic homopolymer.
- the substantially random inte ⁇ olymers are optionally modified by typical
- the polymers may be readily
- the substantially random inte ⁇ olymers are prepared by polymerizing a mixture of
- the substantially random ⁇ -olefin/vinyl aromatic inte ⁇ olymers can also be
- substantially random inte ⁇ olymers which comprise at least
- polymer solution is prepared in a mixture consisting of 50 volume percent 1,1,2,2-
- NMR spectra are acquired at 130°C using an inverse gated
- tail vinyl aromatic monomer preceded and followed by at least one ⁇ -olefin insertion, e.g.
- each Cp is independently, each occurrence, a substituted cyclopentadienyl group
- M is a group IV metal, preferably Zr or Hf, most preferably
- each R is independently, each occurrence, H, hydrocarbyl, silahydrocarbyl, or
- hydrocarbylsilyl containing up to 30 preferably from 1 to 20 more preferably from 1 to
- each R' is independently, each occurrence, H, halo,
- Suitable substituted cyclopentadienyl groups include those illustrated by the formula (VI):
- each R is independently, each occurrence, H, hydrocarbyl, silahydrocarbyl, or
- hydrocarbylsilyl containing up to 30 preferably from 1 to 20 more preferably from 1 to
- R 5 independently each occurrence is (including where appropriate all
- indenyl such as indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, or octahydrofluorenyl.
- catalysts include, for example, racemic-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-oxide
- Any monofunctional azidosilane can be used as the grafting agent for this
- a monofunctional azidosilane is a compound which has one azide group.
- the monofunctional azidosilane is either a sulfonylazidosilane or a
- carbonylazidosilane more preferably a sulfonylazidosilane, most preferably 2-(4-
- the preferred azidosilane compounds have either of the following general
- R 6 is any organic radical; and Z is, independently each occurrence, a hydrogen, an
- organic radical or other hydrolyzable group including, inter alia, alkoxy group, or a
- R 6 is generally selected from the group consisting of hydrocarbon, halo-
- R 6 will have a long
- R 6 will be a divalent radical selected from the group
- alkylene radicals such as the straight chain and branched C, to C 20 more
- alkenyl radicals which include, for instance, the methylene
- ethylene trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene,
- decamethylene dodecamethylene, octadecamthylene, and the like radicals; cycloalkylene
- radicals such as the C 3 to C 20 cycloalkylene radicals which include, for instance, the
- the cycloalkylene will be connected to the silicon atom by a straight chain alkylene of 1 to 20 methylene groups, even more preferably, the cycloalkylene connected
- arylene radicals such as o-, m- and p-
- phenylene, naphthylene, biphenylene, and the like radicals phenylene, naphthylene, biphenylene, and the like radicals; arylene-alkylene radicals,
- alkylene portion consists of a straight chain of 2 to 20 methylene groups
- arylene-dialkylene radicals such as o-, m-, p-xylene diethylene, o-, m-, p-phenylene
- alkylene-diarylene radicals such as methylene bis (o-, m-
- cycloalkylenediakylene radicals such as 1,2- and 1,3- and 1,4- cyclohexanedimethylene
- alkylene radicals arylene-oxy-arylene radicals, aralkylene-oxyarylene radicals,
- alkyarylene-oxyalkarylene radicals aralkylene-oxyoaralkylene radicals and the like; as
- R 6 can contain other functional groups which are substantially inert
- esters such as esters, sulfonate esters,
- R 6 The preferred structure for R 6 are: a straight chain of between 3 to 20 methylene
- Z may be a hydrolyzable radical.
- Typical hydrolyzable radicals are the halo
- radicals which include, for instance, the fluoro, chloro, bromo, and iodo, radicals
- alkoxy radicals including the C, to C 20 straight and branched chain alkoxy radicals
- organo oxycarbonyl radicals such as phenoxy, and the like; the organo oxycarbonyl radicals including the
- aliphatic oxycarbonyl radicals such as acetoxy, propionyloxy, stearoyl oxy, and the like;
- cycloaliphatic oxycarbonyl radicals such as cyclohexylcarbonyloxy, and the like;
- aromatic oxycarbonyl radicals such as benxoyloxy, xyloxy, and the like.
- Z may also be a radical of preferably 1-20 carbons, more preferably 1-5 carbons,
- At least one Z comprises a hydrolyzable group.
- Representative radicals are
- alkyl selected from the group consisting of alkyl, cycloalkyl, aryl, alkaryl, aralkyl radicals such
- Preferred azidosilanes for the practice of this invention have the following
- the melting point of the azidosilane is preferably less than 150 C, more
- the azidosilane is preferably greater than 200 C.
- the decomposition temperature of the azidosilane is preferably greater than 200 C.
- azidosilane is preferably higher than the melting point of the polymer to be grafted, more
- the azidosilane is miscible with the ESI or
- metallocene LLDPE preferably through including a long chain aliphatic component in
- the azidosilane molecule more preferably the long chain aliphatic group is up to 20
- the azidosilane and polyolefin preferably react at a temperature at
- the decomposition temperature is measured by heating a sample (1.5 mg), in a DSC, from a temperature of 20 C to 400 C at a rate of 10
- azidosulfonyl silanes include among others, 5-(trimethoxysilyl)-
- amylsulfonyl azide 4-(triethoxysilyl)-cyclohexylsulfonyl azide, 2-methyl-
- azidosilane compound ⁇ -(azidosulfonyl)-
- the subject matter of the invention includes inco ⁇ orating at least one second
- the second polymer may be any polyolefinic polymer.
- suitable polymers for use as the second polymer include any of the ⁇ -
- olefin vinyl aromatic inte ⁇ olymers HEPs, or SLEPs as described for use as the first
- these ⁇ - olefin/vinyl aromatic inte ⁇ olymers, HEPs, or SLEPs have
- the second polymer can be any other polyolefin, such as polyethylene,
- polypropylene HDPE, LDPE, LLDPE, and the like, made with metallocene, other single-
- polyethylene especially polyethylene, ethylene ⁇ -olefm copolymers or a combination thereof, at least
- the higher average molecular weight is preferably more than
- the resulting blend thus optionally has a Mw/Mn greater
- These polymers include homogeneous linear ethylene polymers such as (a) those
- polymers are TAFMERTM polymers made by Mitsui Petrochemical Industries, Ltd. and
- the second polymer may be inco ⁇ orated with the first polymer either before or
- polymers may be used alone or in combination with one or more additional polymers in a
- polymer blend When additional polymers are present, they may be selected from any of the modified or unmodified homogeneous polymers described above for this invention.
- polymers according to this invention fall into two broad categories, those prepared with a
- the former are
- LDPE low density polyethylenes
- polymers generally have a density between 0.910 and 0.935 g/cc.
- copolymers prepared by the use of a coordination catalyst such as a Ziegler Natta or
- Phillips catalyst are generally known as linear polymers because of the substantial
- High density polyethylene generally having a density of 0.941 to 0.965 g/cc, is
- HDPE high density polyethylene
- LLDPE polyethylene
- ⁇ -olefin 3 to 12 carbon atoms, preferably 4 to 8 carbon atoms (e.g., 1-butene, 1-octene, etc.), that has
- the copolymer contains even more ⁇ -olefin, the density will drop below 0.91 g/cc and
- VLDPE density polyethylene
- linear ethylene polymers are available from The Dow Chemical Company as
- DOWLEXTM LLDPE and as ATTANETM ULDPE resins are included in DOWLEXTM LLDPE and as ATTANETM ULDPE resins.
- polymers can be prepared via the solution, slurry or gas phase polymerization of ethylene
- heterogeneous ethylene polymers are typically characterized as having
- Mw/Mn molecular weight distributions
- the azidosilane is admixed with the polymer and heated to at
- the invention further includes a process for producing a water-curable silane-
- grafted polymer comprising: (A) admixing (i) at least one first polymer, the first polymer selected from the group
- the inte ⁇ olymer comprising polymer units of at least one ⁇ -
- the temperature is advantageously greater than 90 C, preferably greater
- Preferred times at the desired decomposition temperatures are times that are
- reaction time is preferably at least 4 minutes at 200 C.
- the azidosilane is present in an amount greater than 0 percent, preferably at least
- azidosilane addition depends on both the molecular weight of the polymer to be crosslinked and the degree of crosslinking desired.
- the degree of crosslinking is
- invention has a degree of crosslinking of at least 20 percent gel, preferably at least 60
- Admixing of the polymer and grafting agent is conveniently accomplished by any combination of the polymer and grafting agent.
- solubility of the azide in the polymer melt In a blend it is desirable to have low solubility
- Preferred processes include at least one of (a) dry blending the grafting agent with
- the polymer preferably to form a substantially uniform admixture and adding this mixture
- melt processing equipment e.g. a melt extruder to achieve the grafting reaction
- a grafting agent in liquid form e.g. dissolved in a solvent therefor or in a
- the decomposition temperature of the grafting agent preferably by melt blending
- a second admixture of the first admixture with a second amount of a second polymer for example a concentrate of a grafting agent admixed with at least one
- process (c) is conveniently used to make a concentrate with a first polymer composition
- Each polymer or polymer composition includes at least one polymer or polymer composition into the second polymer composition.
- Each polymer or polymer composition includes at least one polymer or polymer composition
- melt processing is used to mean any process in which the polymer is
- polyolefin(s) and grafting agent are suitably combined in any manner which
- decomposition of the grafting agent occurs
- This mixing is preferably attained with the polymer in a molten or melted state
- the molten or melted form is
- Any equipment is suitably used, preferably equipment which provides sufficient
- extruder is used for its broadest meaning to
- step of the process of the invention takes place in the melt extrusion step. While it is
- reaction take place in a solvent or other medium
- reaction be in a bulk phase to avoid later steps for removal of the solvent or other medium.
- a polymer with a crystalline melt temperature for this pu ⁇ ose, a polymer with a crystalline melt temperature
- the vessel as heating to the decomposition temperature of the grafting agent.
- the vessel is
- twin-screw extruder preferably a twin-screw extruder, but is also advantageously a single-screw extruder, a
- the reaction vessel more preferably has at least two zones of different
- the first zone advantageously
- the grafting agents and the second zone being at a temperature sufficient for
- the first zone is preferably at a temperature
- inco ⁇ oration of grafting agent is to solution blend the grafting agent in solution or
- the solvent is preferably a solvent for the grafting agent
- solvents include polar solvents such as acetone, THF (tetrahydrofuran) and chlorinated
- hydrocarbons such as methylene chloride.
- non-polar compounds such as ethylene chloride.
- grafting agent is well blended into the polymer, in alternative preferred embodiments it is
- the grafting agent be added to the post-reactor area of a polymer processing
- the grafting agent is
- the grafting agent is preferably added to the polymer melt stream
- silane-grafted ethylene polymers processes for making them, and
- Such articles comprising the silane-grafted polymer of this invention may be made.
- processing pellets or granules of polymer which have been silane-grafted may include processing pellets or granules of polymer which have been silane-grafted
- the pellets or granules are
- the low density ethylene copolymer preferred embodiments (density less than
- extrusion such as to form wire and cable coatings, tubing, profiles such as gaskets and
- seals sheeting, extrusion coatings such as ca ⁇ et backing, multilayer packaging,
- the low density preferred embodiments are
- compositions. Film and film structures particularly benefit from this invention and can be made
- Biaxial orientation film manufacturing process such as
- structures can also be made as described in a tenter-frame technique, such as that used for
- the films may be monolayer or multilayer films.
- invention can also be coextruded with the other layer(s) or the film can be laminated onto
- tubular film i.e., blown film techniques
- flat die i.e., cast film
- the film is a coextrusion of two or more
- the film may still be laminated to
- coextruded films can also go through other post extrusion techniques, such as a biaxial
- Extrusion coating is yet another technique for producing multilayer film structures
- novel compositions comprise at least
- extrusion coating is a flat die
- a sealant can be extrusion coated onto a substrate either in the form of a
- multilayer structure include but are not limited to barrier layers, and/or tie layers, and/or
- Some of these materials include:
- PVDC polyvinylidene chloride
- PET polyethylene terephthalate
- OPP oriented polypropylene
- EVA ethylene/vinyl acetate copolymers
- EAA ethylene/acrylic acid copolymers
- EMAC graft adhesive polymers
- structures comprise from 2 to 7 layers.
- silane-grafted polymers of this invention are water curable. That is, in the
- crosslink refers to the attachment of two chains of polymer molecules by bridges
- R 7 and R 8 are any organic radicals having a nitrogen which is attached by a primary
- the organic radicals R 7 and R 8 are
- azidosilanes as grafting agents, especially where the different azidosilanes have different
- the water can be introduced to the silane-grafted polymer as vapor, steam, liquid
- the curing can optionally and preferably be carried out in the presence of a silanol
- condensation catalyst Such catalysts are known in the art. Such materials include metal
- carboxylates such as dibutyltin dilaurate, organic bases such as ethylamine, hexylamine,
- the catalyst is a metal carboxylate, more preferably dibutyltin
- thermomechanical analyzer is used to measure the
- Probe force of 102g and heating rate of 5°C/min were used.
- Each test specimen is a disk with thickness of 2 mm and a diameter of 7 mm prepared by
- the melt index is measured according to ASTM-D-1238 Condition 190
- sample baskets are removed and placed in a vacuum oven at 150°C and 28 in. of Hg vacuum for 12 hours. After 12 hours, the samples are removed,
- Samples are prepared using either a mixer commercially available from Haake,
- the copolymer contains 10.88 mole
- polymer contains less than 1 weight percent homopolymer polystyrene impurity.
- the copolymer contains 15.8 mole percent
- the sample contains less than 1 weight percent homopolymer polystyrene impurity.
- the sample has a
- melt index of 1.3 g/10 min. ES41 is prepared as described below.
- the copolymer contains 21.9 mole percent
- the sample contains less than 1 weight percent homopolymer polystyrene impurity.
- the sample has a
- ES51 is prepared as described below.
- the copolymer contains 27.1 mole percent
- the sample has a melt index of 1.0 g/10 min.
- ES58 is prepared as described below.
- the copolymer contains 37.5 mole percent
- the sample contains 2 weight percent homopolymer polystyrene impurity.
- the sample has a melt
- ES69 is prepared as described below.
- the copolymer contains 40.9 mole percent
- the sample contains 3 weight percent homopolymer polystyrene impurity.
- the sample has a melt
- ES72 is prepared as described below.
- the copolymer contains 42.6 mole percent
- sample also contains 8.6 weight percent homopolymer polystyrene as an impurity.
- the sample also contains 8.6 weight percent homopolymer polystyrene as an impurity.
- Ethylene Styrene Inte ⁇ olymers ESI
- CSTR CSTR
- impellers provides the mixing.
- the reactor ran liquid full at 475 psig (3,275 kPa).
- Process flow is in the bottom and out the top. A heat transfer oil is circulated through the
- Solvent ethylbenzene or toluene
- psig 207 kPa
- the feed to the reactor was measured by a mass flow meter.
- a variable speed diaphragm A variable speed diaphragm
- Uninhibited styrene monomer is supplied to the reactor at 30 psig (308
- the feed to the reactor is measured by a mass flow meter.
- diaphragm pump controls the feed rate.
- the styrene stream is mixed with the remaining solvent stream.
- Ethylene is supplied to the reactor at 600 psig (4,238 kPa). The ethylene
- meter controller is used to deliver hydrogen into the ethylene stream at the outlet of the
- the ethylene/hydrogen mixture combines with the solvent/styrene
- This solvent/styrene stream enters the bottom of the reactor.
- This effluent stream next entered post reactor heaters that provide additional energy for
- volatiles oil jacketed devolatilizer. Approximately 85 percent of the volatile compounds (hereinafter volatiles) are removed from the polymer in the devolatilizer. The volatiles
- Solvent and styrene are removed from the bottom of the vessel and ethylene from the top.
- the ethylene stream is measured with a flow meter and analyzed for composition.
- This strand is cooled as it is pulled through a water bath. The excess water is
- SCCM means standard cubic centimeter "Cocat Bor” refers to the boron containing co-catalysts which are bis-
- Catalyst type 1 is
- Catalyst type 2 is dimethyl[N-(l,l-dimethylethyl)-l,l-dimethyl-l-[(l,2,3,4,5-.eta.)-
- MMAO A modified methylaluminoxane commercially available from Akzo
- MMAO-3A was used.
- Vinyltrimethoxysilane [2 C.I. No.768-02-7] was purchased from Aldrich and used
- Dibutyltin dilaurate [C.I. No. 77-58-7] was purchased from Aldrich and used as
- Dicumyl peroxide [C.I. No. 80-43-3] was purchased from Hercules Inc. under the
- the filtrate is concentrated by rotary evaporation (bath - 30°C) to yield 8.7 g of a white solid (product + NaCl).
- the residue is slurried in methylene chloride and then filtered.
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2001515721A JP2003506533A (en) | 1999-08-09 | 2000-08-01 | Azidosilane-modified moisture-curable polyolefin polymer, production method, and articles obtained therefrom |
AU65069/00A AU6506900A (en) | 1999-08-09 | 2000-08-01 | Azidosilane-modified, moisture-curable polyolefin polymers, process for making, and articles obtained therefrom |
EP00952354A EP1218422A1 (en) | 1999-08-09 | 2000-08-01 | Azidosilane-modified, moisture-curable polyolefin polymers, process for making, and articles obtained therefrom |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US09/370,309 US6331597B1 (en) | 1999-08-09 | 1999-08-09 | Azidosilane-modified, moisture-curable polyolefin polymers, process for making, and articles obtained therefrom |
US09/370,309 | 1999-08-09 |
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Publication Number | Publication Date |
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WO2001010914A1 true WO2001010914A1 (en) | 2001-02-15 |
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PCT/US2000/020912 WO2001010914A1 (en) | 1999-08-09 | 2000-08-01 | Azidosilane-modified, moisture-curable polyolefin polymers, process for making, and articles obtained therefrom |
Country Status (6)
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US (1) | US6331597B1 (en) |
EP (1) | EP1218422A1 (en) |
JP (1) | JP2003506533A (en) |
CN (1) | CN1368981A (en) |
AU (1) | AU6506900A (en) |
WO (1) | WO2001010914A1 (en) |
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102007060536A1 (en) | 2007-12-13 | 2009-06-18 | Henkel Ag & Co. Kgaa | Coating agent with double crosslinking |
WO2009074365A1 (en) * | 2007-12-13 | 2009-06-18 | Henkel Ag & Co. Kgaa | Coating agent with double cross-linking |
US8211549B2 (en) | 2007-12-13 | 2012-07-03 | Henkel Ag & Co. Kgaa | Coating agent with double cross-linking |
DE102008040886A1 (en) | 2008-07-31 | 2010-02-04 | Wacker Chemie Ag | Click-reaction crosslinkable multicomponent silicone compositions |
EP2151467A1 (en) | 2008-07-31 | 2010-02-10 | Wacker Chemie AG | Click-reaction crosslinkable multicomponent silicone compositions |
US8071708B2 (en) | 2008-07-31 | 2011-12-06 | Wacker Chemie Ag | Click-reaction crosslinkable multicomponent silicone compositions |
US8572903B2 (en) | 2010-01-28 | 2013-11-05 | The Sherwin-Williams Company | Device, kit and method for sealing roof penetrations |
CN105349020A (en) * | 2015-02-20 | 2016-02-24 | 上海埃菲东多胶粘技术有限公司 | Low viscosity moisture cured polymer compositions with tensile and creep properties for Industrial coatings,adhesives and sealant applications |
CN109752495A (en) * | 2019-03-20 | 2019-05-14 | 广州质量监督检测研究院 | The detection method of wood furniture smell |
Also Published As
Publication number | Publication date |
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AU6506900A (en) | 2001-03-05 |
CN1368981A (en) | 2002-09-11 |
EP1218422A1 (en) | 2002-07-03 |
JP2003506533A (en) | 2003-02-18 |
US6331597B1 (en) | 2001-12-18 |
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