GB1565674A - Creation of Inventions and Patents with Artificial Intelligence

GB1565674A – Crosslinkable porous polymer powder and laminate
– Google Patents

GB1565674A – Crosslinkable porous polymer powder and laminate
– Google Patents
Crosslinkable porous polymer powder and laminate

Download PDF
Info

Publication number
GB1565674A

GB1565674A
GB41932/76A
GB4193276A
GB1565674A
GB 1565674 A
GB1565674 A
GB 1565674A
GB 41932/76 A
GB41932/76 A
GB 41932/76A
GB 4193276 A
GB4193276 A
GB 4193276A
GB 1565674 A
GB1565674 A
GB 1565674A
Authority
GB
United Kingdom
Prior art keywords
composition according
crosslinkable composition
polymer
powder
polymeric material
Prior art date
1975-10-22
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)

Expired

Application number
GB41932/76A
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

ExxonMobil Technology and Engineering Co

Original Assignee
Exxon Research and Engineering Co
Priority date (The priority date 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 date listed.)
1975-10-22
Filing date
1976-10-08
Publication date
1980-04-23

1976-10-08
Application filed by Exxon Research and Engineering Co
filed
Critical
Exxon Research and Engineering Co

1980-04-23
Publication of GB1565674A
publication
Critical
patent/GB1565674A/en

Status
Expired
legal-status
Critical
Current

Links

Espacenet

Global Dossier

Discuss

Classifications

C—CHEMISTRY; METALLURGY

C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR

C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR

C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers

C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment

C09D127/04—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms

C09D127/06—Homopolymers or copolymers of vinyl chloride

C—CHEMISTRY; METALLURGY

C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON

C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H

C08J3/00—Processes of treating or compounding macromolecular substances

C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules

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

C08K5/14—Peroxides

C—CHEMISTRY; METALLURGY

C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR

C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers

C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment

C09D123/04—Homopolymers or copolymers of ethene

C09D123/08—Copolymers of ethene

C—CHEMISTRY; METALLURGY

C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR

C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers

C09D151/06—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

C—CHEMISTRY; METALLURGY

C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR

C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes

C09D5/03—Powdery paints

C09D5/033—Powdery paints characterised by the additives

Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC

Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

Y10T428/00—Stock material or miscellaneous articles

Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof

Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]

Y10T428/2991—Coated

Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]

Y10T428/2995—Silane, siloxane or silicone coating

Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC

Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

Y10T428/00—Stock material or miscellaneous articles

Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof

Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]

Y10T428/2991—Coated

Y10T428/2998—Coated including synthetic resin or polymer

Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC

Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

Y10T428/00—Stock material or miscellaneous articles

Y10T428/31504—Composite [nonstructural laminate]

Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]

Y10T428/31609—Particulate metal or metal compound-containing

Y10T428/31612—As silicone, silane or siloxane

Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC

Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

Y10T428/00—Stock material or miscellaneous articles

Y10T428/31504—Composite [nonstructural laminate]

Y10T428/31652—Of asbestos

Y10T428/31663—As siloxane, silicone or silane

Description

PATENT SPECIFICATION
( 11) ( 21) Application No 41932/76 ( 22) Filed 8 Oct 1976 ( 31) Convention Application No624 959 ( 19) ( 32) Filed 22 Oct 1975 in ( 33) United States of America (US) ( 44) Complete Specification published 23 April 1980 ( 51) INT CL 3 C 08 J 3/24 I ( 52) Index at acceptance C 3 J 356 AC B 2 E 1205 1730 415 S 422 T 460 T 470 T 473 T 474 T 475 T 476 T 479 T 480 T 489 T 490 T 493 T BDB C 3 C 100 103 107 110 153 181 350 351 369 372 373 375 385 451 452 454 546 551 554 556 C 3 W 207 D 209 209 B 209 C 212 B 216 216 D 217 217 D 218 218 D C 3 Y B 200 B 210 B 230 B 240 B 241 B 242 B 245 B 262 B 284 B 286 B 390 F 104 G 200 H 100 ( 72) Inventors ROBERT ADRIAN VAN BREDERODE and ROBERT ANDREW STEINKAMP ( 54) CROSSLINKABLE POROUS POLYMER POWDER AND LAMINATE ( 71) We, EXXON RESEARCH AND ENGINEERING COMPANY, a Corporation duly organised and existing under the laws of the State of Delaware, United States of America, of Linden, New Jersey, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed to be particularly described in and by the
following statement:-
This invention relates to finely divided normally solid, porous, synthetic organic polymeric thermoplastic resins.
is Thermoplastic polymers in powder or finely divided form have a wide variety of commercial applications, such as for example, the dry powders have been used to coat articles in dry form by dip coating in either static or fluidized beds, by electrostatic coating, spraying or dusting and flame spraying The powders are used in dispersed form in suitable liquid carriers to apply coatings by roller coating, spray coating, and dip coating to a variety of substrates such as: glass, ceramics, metal, wood, cloth, paper, paperboard, and the like The finely divided polymers have also been successfully employed in conventional powder molding techniques The fine powders have also been applied as paper pulp additives, mold release agents, wax polish, paint compositions, binders for non woven fabrics and finishes for woven fabrics.
There are basically four types of processes employed in the prior art for preparing finely divided polymer particles, i.e, mechanical grinding, solvent precipitation, dispersion and spray atomization of solutions or slurries.
Generally mechanical grinding employs conventional equipment to yield particles of irregular shape and wide size variation of from about 75 to 300 microns The powders produced by this method may not be suitable for applications where free flowing powders are required, since the irregular shapes may inhibit the flowability of these powders The grinding of some polymer may be very costly because of the toughness of the resin even when cryogenically cooled.
Spray techniques are generally satisfactory for producing uniform nonagglomerated, spherical particles, however, very specialized equipment, usually nozzles operating under a limited range of conditions to prevent nozzle plugging are required Substantial problems in spraying are the shearing of the polymer as it passes through the nozzle, premature precipitation of the polymer or rapid volatilization of solvent.
The dispersion method also is subject to high shear conditions Frequently water is the dispersing medium and dispersing agents are used to facilitate the dispersion.
Hence the powders produced by this technique generally incorporate some or all of the dispersing agent in the powder which can create undesirable changes in the original polymer properties, e g, increased water sensitivity, loss of electrical insulating values, loss of adhesive capabilities, etc.
cc nt 1565674 1,565,674 Another type of prior art process generally entails dissolving the polymer in a solvent, followed by precipitation of the polymer in finely divided form through addition of a nonsolvent, cooling or evaporation of the solvent or a combination of the above Problems in this process have included difficulty in manipulating the solvents, solvent removal, particle agglomeration which requires a great deal of grinding, and particles having irregular somewhat rounded shapes.
Grinding or emulsification of a polymer melt produces non-porous powder particles.
Coating of substantially non-porous substrates such as glass or metal has frequently been characterized by poor surface bonding or poor resistance of the bond to certain environments Nonreturnable glass bottles have been covered with polystyrene or polyethylene jackets or ionomer resin to reduce breakage and retain fragments if broken, however, these coatings are not intended to be permanently bonded Even when a bond is obtained, it is usually the case that the resin or bond will not withstand the caustic rinses at 150 to 1600 F which are used on returnable bottles.
The objectives of placing polymer coatings on returnable bottles is to reduce scratches and impact on the glass and hence increase the useful life of each bottle The coating should also provide a safer bottle, reducing the likelihood of breakage, and in the event of breakage, contain the shattered glass or a portion thereof within the plastic skin.
The present invention therefore provides a crosslinkable powder comprising a major amount of porous particles of an organic theremoplastic polymeric material said particles being less than 100 microns in size and said polymeric material having a decomposition temperature higher than 1000 C and having sorbed therein a minor amount of an organic peroxide.
For certain polymeric materials, there also can be a minor amount of an organo functional silicon compound Another facet of the invention in those instances where silanes are used are the laminate compositions resulting from application of the powder compositions Generally, when the appropriate silanes are used, the resulting fused coatings are especially resistant to alkaline hydrolysis at elevated temperatures The powder composition of the invention is particularly useful for electrostatic coatings Preferably the powders are less than 74 microns in particle size (diameter) and generally are from 15 to 70, preferably 15 to 40 and most preferably 18 to 35 microns average diameter The crosslinking agent, e g, peroxide, serves to initiate crosslinking of the powder when it is fused, and it has been discovered by the present inventors and forms a facet of the invention, that it should be distributed as evenly as possible on each powder particle.
It has been discovered that this can be achieved by sorbing the crosslinking agent, e.g, organic peroxide, into the porous powder preferably into each of the individual porous polymer powder particles.
The use of a porous powder allows more uniform distribution of the peroxide (and the silane if used) to give a greatly improved coating and as such is an important aspect of this invention The presence of residual or grafted ethylenic unsaturation may aid in the crosslinking of the powders and is optional.
The present compositions will generally contain 99 9 to 96 0 weight % polymeric powder, 0 05 to 2 0 weight percent organic peroxide and 0 05 to 2 0 weight percent organosilicon compound, preferably up to 1.0 weight percent each of the organic peroxide and the organosilicon compound and between 98 and 99 9 weight percent of the polymeric powder.
The organosilicon compound serves to improve the adhesion of the polymer to the glass or metal substrate The organosilicon compound may not be necessary to develop or maintain adhesion, when the polymer itself has sufficient adhesive character, such as functionally grafted and random copolymers using such functional monomers as acrylic acid or glycidyl acrylate Hence, compositions containing only powdered porous, organic polymeric material of these types and an organic peroxide with no silane present are contemplated, containing from 99 95 to 98 0 weight percent polymeric material and 0 05 to 2 0 weight percent organic peroxide.
1051 IN THE DRAWINGS:
Fig 1 is a graph comparing the stressstrain curves for crosslinked and uncross 110 linked polymer coating.
Fig 2 is a laminate of glass and a crosslinked polymer powder according to the present invention.
In general the powders suitable for the 115 practice of the present invention are prepared from polymers which include any normally solid synthetic organic polymeric thermoplastic resin whose decomposition point is somewhat higher than 1000 C 120 Included are polyolefins, vinyls, olefin-vinyl copolymers, olefin-allyl copolymers, polyamides, acrylics, polystyrene, cellulosics, polyesters, and polyhalocarbons such as polyfluorocarbons 125 Generally the most suitable polyolefins for use in the present process include normally solid polymers of mono-alphaolefins, which comprise from 2 to 6 carbon 1,565,674 atoms, for example, polyethylene, polypropylene, polybutylene, polyisobutylenes, poly ( 4-methylpentene-1), and copolymers of these various alpha-olefins.
Vinyl polymers suitable for use herein include polyvinyl chloride, polyvinyl acetate, vinyl chloride/vinyl acetate copolymers, polyvinyl alcohol and polyvinyl acetal.
Among the suitable olefin-vinyl copolymers are ethylene-vinyl acetate, ethylene-vinyl propionate, ethylene-vinyl isobutyrate, ethylene-vinyl alcohol, and ethylene-methyl acrylate Olefin-allyl copolymers include ethylene-allyl alcohol, ethylene-allyl acetate, ethylene-allyl acetone, ethylene-allyl benzene, and ethylene-allyl ether.
Examples of some specific acrylic polymers are poly(methyl metahcrylate), poly(acrylonitrile), poly(methylacrylate) and poly(ethylmethacrylate) The polyamides suitable for use include polyhexamethylene adipamide, polyhexamethylene sebacamide, and polycaprolactam.
The process used to prepare the powders is suitable also for mixtures of thermoplastic polymers such as ethylene-vinyl acetate/polyethylene and polyethylene/polypropylene, mixtures.
The powders may also be prepared from a solvent reaction system wherein the polymeric material is prepared in a solvent system, such as for example the alpha-olefin polymers, as described in numerous patents such as U S 3,112,300; U S 3,113,115; U S.
3,197,452; Belgian Patent 538,782 and British Patent 994,416 Catalysts are the now well known “Ziegler” variety.
A variety of monomers may be polymerized with the Ziegler type catalysts.
Any unsaturated hydrocarbon corresponding to the general formula R-C=CH 2, wherein R is selected from the group consisting of an alkyl radical having from one to six carbon atoms, a phenyl radical, or an alkyl substituted phenyl radical can be used Examples of specific unsaturated hydrocarbons which can be polymerized include alpha-olefins containing 3 to 8 carbon atoms, such as propylene, butene, isobutylene, pentene, isoamylene, hexene, isohexenes, heptene, isoheptenes, octene and isooctenes.
The monomers may be polymerized at moderate temperatures and pressures with the Ziegler type catalysts described above, generally at temperatures of O C to 150 C, with temperatures on the order of 25 C to C being particularly useful A solvent such as paraffin or cycloparaffin having 3 to 12 carbon atoms, may be employed for the polymerizations, however, the olefin monomer is frequently used for this purpose The polymerizations are preferably conducted under conditions that exclude atmospheric impurities such as moisture, oxygen and the like.
The pressure ranges from about 70 atmospheric pressure to several atmospheres with pressures in excess of about 500 psi rarely being employed.
After the polymer has been produced, the catalyst is deactivated by contacting the 75 polymeric reaction mixture with a material which reacts with and deactivates the catalyst Such materials include, for example, lower alcohols, acetone and water.
The term polyolefins includes those 80 materials modified with materials such as the unsaturated organic acids, for example, maleic acid, muconic acid, dimethyl muconic acid, acrylic acid, methacrylic acid, and vinyl acetic acid Generally the 85 polyolefins may be modified by from I to 10 weight percent of the unsaturated acid The modification has been observed to improve the surface adhering characteristics of the polyolefin polymers when they are 90 employed as surface coating, particularly the alpha-olefins, such as polypropylene.
The modifying unsaturated acids may be incorporated into the polyolefins by intimately contacting the modifier with the 95 polyolefin in a melt or solution of the polymer in the presence of a free radical source, such as an organic peroxide The modifying unsaturated acid may also be randomly copolymerized with a poly 100 merizable olefin, such as ethylene, and neutralized or partially neutralized to yield an ionomer.
In the process of preparing powders for the present invention it is possible to employ 105 graft polymers prepared by known methods in the art, e g, those to be found in U S.
Patents 3,177,269; 3,177,270; 3,270,090; 3,830,888; 3,862,265; British 1,217,231 and British 679,562 110 The preferred modifying monomers which are grafted to the backbone or copolymerized with ethylene are C 3 to C 10, preferably C 3 to C 6 unsaturated mono and polycarboxylic unsaturated acids, 115 anhydrides, salts, esters, ethers, amides, nitriles, thio, glycidyl, cyano, hydroxy, glycol, and other substituted derivatives thereof.
Examples of such acids, anhydrides and 120 derivatives thereof include maleic acid, fumaric acid, itaconic acid, citraconic acid, acrylic acid, glycidyl acrylate, cyano ethyl acrylate, hydroxyethyl methacrylate, acrylic polyethers, acrylic anhydride, methacrylic 125 acid, crotonic acid, isocrotonic acid, mesaconic acid, angelic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, sodium acrylate, calcium acrylate, and magnesium acrylate 130 1,565,674 Other monomers which can be used either by themselves or in combination with one or more of the carboxylic acids or derivatives thereof include C 8 to C 5 o vinyl monomers such as monovinyl aromatic compounds, i e styrene, chlorostyrenes, bromostyrenes, alpha-methyl styrene and the like.
Other monomers which can be used are C 8 to C 50 vinyl esters and allyl esters, such as vinyl butyrate, vinyl laurate, vinyl stearate, and vinyl adipate, and monomers having two or more vinyl groups, such as divinyl benzene, ethylene dimethacrylate, triallyl phosphite, dialkylcyanurate and triallyl cyanurate.
The present invention is especially useful for grafted polymers prepared by grafting a polymer of a C 2 to C 8 mono-a-olefin or its copolymers with acrylic acid in a special process The polymers of C 2 to C 8 mono-caolefins are commonly referred to as polyolefins and for the purpose of this invention are to include copolymers of the C 2 to C 8 mono-alpha-olefins with each other and with other monomers as well as the homopolymers.
Polymers containing diolefins such as butadiene and isoprene are also suitable.
The polyolefins are produced utilizing in most instances a Ziegler-type catalyst, but Phillips catalysts and high pressure technology can also be used.
Examples of suitable thermoplastic polyolefins include low or high density polyethylene, polypropylene, polybutene-1, poly-3-methylbutene 1, poly-4-methylpentene-l, copolymers of monoolefins with other olefins (mono or diolefins) or vinyl monomers such as ethylene-propylene copolymers or with one or more additional monomers, i e EPDM, ethylene/butylene copolymer, ethylene/vinyl acetate copolymer, ethylene/ethyl acrylate copolymer, propylene/4-methylpentene-1copolymer and the like.
The preferred grafted polyolefins employed in the present invention contain propylene and/or ethylene, i e polypropylene and polyethylene The starting polymer used as a base material in the graft process will preferably have a melt index (MI) ASTM D-1238-65 T of I to 40, preferably 15 to 40, and most preferably 20 to 30, or melt flow rate (MFR) from 0 1 to and preferably 0 5 to 10, most preferably 2 to 5 The melt flow rates correspond approximately to viscosity average molecular weights of 100,000 to 500,000.
The preferred monomers to be grafted to the C 2 to C 8 polyolefin and other polymers for use in the present invention are maleic anhydride, acrylic acid, methacrylic acid, glycidyl acrylate, hydroxyethyl methacrylate and their derivatives Others that can be used are described elsewhere herein.
However, other monomers may be added in admixture with these such as maleic anhydride (MA), styrene, acid esters, salts and the like to form graft copolymers MA and styrene and MA and acrylic acid are preferred over MA alone when polymer grafts of MA are desired.
The powder is preferably prepared from the polyolefin by dissolving the polymer in a solvent, cooling the solution to precipitate the polymer and drying the resulting slurry by atomization as described in United States Patent 4012461 The porous powder that results allows for better distribution of additives As a result, a product with more uniform crosslinking and adhesion is produced This can result in significantly better mechanical properties of the film coating and better adhesion Other powder making techniques such as grinding and emulsification produce non-porous powder which has the following disadvantages among others: the additives would cover the surface only and do not penetrate into the polymer; the additives which have been belt mixed prior to powder making to incorporate them into the polymer may be rendered inactive by high temperatures used in emulsification of the mix; grinding of such melt mixed polymer and additives is not economically or technically suitable for producing the necessary fine powder particles.
The solvents employed in the preferred powder making technique are preferably paraffins or cycloparaffins having 5 to 12 carbon atoms Suitable solvents include npentane, isopentane, n-heptane, isooctane, cyclohexane, methycyclohexane, and nonane, or mixtures of solvents The solvent will generally contain from 1 to 40 weight percent, more preferably 5 to 20 weight percent of polymer based on the total weight of the solution.
About 15 weight percent of the polymer is dissolved in the solvent, for example nheptane, by heating at 100 to 140 C.
preferably in the range of 110 to 130 C.
under autogenous pressure for 5 minutes to 2 or more hours, typically about 1 hour.
Preferably the temperature is selected to maintain the pressure in the autoclave at less than 75 psig, more preferably less than psig Both ethylene and propylene based polymers dissolve under these conditions.
The slurry is produced by cooling the solution to a temperature below 90 C.
Polymer precipitation begins at about 90 C.
and continues as the temperature is lowered, at a rate of 1 to 10 C /minute, preferably about 5 C /minute.
The temperature of the solution is lowered to about 50 C Lower temperatures may be used but are not necessary, similarly 1.565 674 temperatures from 20 ‘C up to about 80 WC.
are suitable for the final slurry temperature.
It is readily apparent that at temperatures above 200 C, somewhat larger amounts of polymer will remain dissolved in the solvent, unless long precipitation periods are provided In any event, it is necessary to keep the residual polymer, which is dissolved in solution, below the concentration which will produce strings as the solvent is atomized along with slurry particles.
Thus since it is desirable to remove solvent from the slurry particles, operation of the process should be carried out such that there is less than that amount of the polymer remaining in solution in the solvent than will inhibit formation of droplets at the drying zone temperature The amount of polymer which may remain in solution in a solvent which has a vapor pressure of 50 to 400 mm of mercury at the temperature of the drying zone is that amount which produces a viscosity in the solvent of no greater than 5 centipoise at the temperature of atomization The particular lower or final precipitation temperature will have to e determined for each solvent and polymer employed to achieve this result.
This can be experimentally determined or may be available in standard technical and engineering tables in regard to some combinations Lengthened precipitation periods may also be used to remove larger amounts of polymer from solution at a given temperature.
The cooling and precipitation is conducted in an agitated solution This aids cooling and speeds precipitation However, the nature of the agitation is quite critical.
The prior art believed that shearing of solution encouraged the formation of polymer strings and thus sought to avoid all agitation to prevent this undesirable result.
However, surprisingly it has been found that high shear does not result in strings.
The precipitation may be carried out in a vessel which is fully baffled Turbine agitators, typically 1/3 to 2/3 the diameter of the vessel have been used, operated with good results at from 20 to 300 rpm.
Satisfactory high shear agitation can be obtained with paddle diameter of from 30 to percent of the internal diameter of the vessel.
The power used to rotate the turbine shaft is typically 4 to 10 horse power per 1,000 gallons of material to be agitated This is qualitatively defined as “intense” agitation.
The shear is high, due both to the intense agitation and the turbine impellers which exhibit intense shear Thus the problem observed in the prior art attributing the production of polymer strings to shearing, is overcome by intensifying the degree of shear to a very high degree, short of emulsification.
The terms defining agitation and shear are qualitative but nonetheless, do provide those of skill in the art with information to carry out the process when coupled with the conditions of operation The optimum results of the present process are obtained at 250 to 300 rpm The degree of shearing necessary to carry out the process is less than that which would be achieved if an emulsion were produced.
An emulsion of the precipitated polymer is not necessary but it is possible Thus the present shearing may be described as less than that necessary to produce an emulsion of polymer particles in the solvent, but by conventional chemical engineering practice the agitation is intense as measured by energy input per unit volume of liquid.
The precipitated particles form a slurry in the precipitation vessel This slurry is removed (by gravity, pumping, pressure, screw, etc) and atomized through a conventional nozzle or centrifugal atomizing wheel such as that provided by Niro Atomizer, Ltd into a vaporization zone, into which a drying gas is being fed at a temperature of 80 to 160 WC, depending on the polymer and solvent, to produce powder particles leaving the vaporization zone at temperatures generally in the range of 30 to 500 C and having about 5 to 30 weight percent solvent still associated therewith.
The damp powder is then dried to the desired condition, for example by fluidized bed, vibrating tray, tumbling or the like.
The vaporizing gas may be air, however, explosive mixtures may result with the powder or solvent Preferably inert gases such as nitrogen, CO 2, or helium are employed.
Generally the particles produced according to this method have a size of less than 100 microns, usually over 99 ‘ of the particles are less than 75 microns.
Some powder, for example, propylene resins (polypropylene, ethylene propylene copolymers, blends of propylenes with ethylene propylene rubber and high density polyethylene and acrylic acid grafted modifications thereof having melt flow rates of 2 to 80) tend to be made of 20 to 30 % agglomerates as taken from the vaporization zone, with the remainder being less than 100 microns, e g, less than 74 microns; the average size being about 30 microns Other powders, for example ethylene resins (polyethylene, ethylene-vinylacetate) tend to form fewer agglomerates as taken from the vaporization zone.
The agglomerates are readily reduced to finer powder by attrition, for example, by impingement mill (particle on particle) or pin mill, such that the yield of particles of less than 100 microns approaches 99 %’ or more The milled agglomerate particles are porous and irregularly spherical, but not sharply angular or elongated as with grinding.
The usual particle size in the absence of agglomeration is less than 100 microns, however, the powders are usually classified to remove any oversized particles, e g, agglomerates, scale, trash, etc and to separate the powders for different uses.
While peroxides and optionally silanes are the primary additives, it has also been found that other additives such as stabilizer, antioxidants, coloring agents and the like may conveniently be added to the solution of polymer, before or during precipitation and slurry stages or during or after the drying step Soluble or dispersable additives are very evenly distributed throughout the powders.
The organic peroxide is a free radical initiator which causes or accelerates the crosslinking when the ethylene polymer powder is fused, for example, to a substrate.
Suitable organic peroxides include benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di(t-butyl peroxy) hexane, di-ethyl peroxide, and acetyl peroxide The peroxide should be selected with care to avoid those which are explosive under the conditions of preparation, storage or use of the powders, and those subject to explosion by shock 2,5dimethyl-,5-di(t-butyl peroxy) hexane has been found to be easily applied to the powder, dried thereon and apparently is not particularly hazardous in the compositions of the present invention The peroxide may be added to the precipitated polymer slurry or preferably to the partially dried powder as a liquid It is advantageous to add the peroxide diluted with solvent while the powder is still somewhat damp to provide better dispersion into the powder pores.
Alternately the peroxide may be added to the completely dry powder in a separate operation providing sufficient dispersion ol the peroxide is achieved such as by diluting the peroxide with a solvent that will wet the polymer and penetrate the porous structure.
The organosilicon compounds utilized are silanes, which may have one to four organic radicals attached to silicon, in particular one or more organic radical terminates with a vinyl, amine, methacrylate, epoxy or chloropropyl group which may react with available reactive groups of the polymer powder Silanes having vinyl functionality are particularly preferred in conjunction with a peroxide when the polymer contains no available reactive groups such as polyethylene, vinyl acetate copolymer or polypropylene.
Compositions of the present invention can be used to from superior coatings for glass bottles in providing protection and safety and adhering to the bottles when cleansed and caustic rinsed.
In addition to the essential components of the present composition other conventional materials may be added thereto, such as fumed silica or talc to improve flow characteristics.
The compositions of the present invention may be crosslinked by heating at a temperature of 150 to 2501 C for a sufficient time, generally 0 5 to 5 minutes to obtain the desired degree of crosslinking The crosslinking may be accelerated by using more peroxide or even small amounts of accelerators, such as N,N-dimethylaniline.
Comparative Examples 1-4 In these examples acrylic acid modified (about 4 % acrylic acid by weight) polyethylene, polypropylene and EVA were dissolved in heptane under autogenous pressure at about 1200 C and cooled to about 551 C under conditions of high shear agitation.
The slurry was sprayed through a Niro centrifugal atomizer having the drying gas entering the spray chamber through a dispenser concentric about the atomization wheel through which the slurry is atomized.
Spherical particles of which 99 % were smaller than 75 microns were recovered with attrition of the agglomerates The conditions of atomizing and the spraychamber are set out in Table I below.
The process was also applied to ethylenevinyl acetate copolymer and ethylene-vinyl acetate-acrylic acid terpolymer The process is also applied to non-grafted polypropylene Each polymer was generally employed as described above and materials were produced in the MI range of from 0 5 to 40 with 99 +% of the powder of less than 74 microns and the weight average particle size of about 20 microns as collected from the spray drier and attrited to remove agglomerates The powders did not require any dusting powders, such as fumed silica for handling, but these could have been added if desired Bulk density was about 0.45 grams/cc for the ethylene polymers and 0.3 grams/cc for the propylene resins.
Polyethylene modified with 0 28 % himic anhydride graft was also prepared in fine powder form as well as a polyethylene0.29 % himic anhydride graft that had been esterified with a glycol ester and polyethylene-2 % glycidyl acrylate copolymer (all percents herein are by weight unless otherwise indicated) himic anhydride is the Diels-Alder addition product of maleic anhydride and cyclopentadiene.
6 I 1,565,674 Examples 1-4
In these examples porous polymer powders ( 20-25 micron weight average size) of an ethylene/vinyl acetate copolymer containing 5 9 % vinyl acetate and modified with 0 5 % acrylic acid was prepared according to the procedure of comparative Examples 1-4 and impregnated according to this invention using methanol as a carrier with varying amounts of 2,5-dimethyl 2; 5di(t-butyl-peroxy) hexane The molded properties were evaluated using 10 mil compression molder pads heated for a total of 4 minutes at the temperature specified in Table II according to ASTM D-142 In addition to the improved mechanical properties, the maximum useful temperature before the polymer flows out is increased for a primary crosslinked resin above that of the non-crosslinked polymer.
The improvement in toughness is vividly demonstrated in Figure 1, where the stress/strain curve for a crosslinked EVA/AA resin is compared to that same resin without peroxide.
TABLE I
Slurry Drying Gas (Nitrogen) Feed Rate Type Temp.
C.
Rate cfm Inlet Temp.
C.
Outlet Temp.
C.
11 % (polyethylene modified with 24 % acrylic acid) in heptane 18 % (ethylene vinyl acetate 5.6 % vinyl acetate modified with 24 % acrylic acid) in heptane 9 % (polypropylene modified with r 6 % acrylic acid) in heptane 9 % (ethylene/vinyl acetate 5.6 vinyl acetate) (MI 25) in heptane 0.5 lb/min 55 1.5 lb/min 55 0.5 lb/min 99 + % finer than 74 microns without attrition.
-.3 Comparative Example
1 lb/min Powder Volatiles % Product Powder Kg/hr.
1.8 5.5 3.4 2.2 1.8 Mechanical Properties @ Break Weight Percent Peroxide % (by addition) 0.25 Molding Temp, 0 F.
400 400 375 325 Tensile Strength (kg/cm 2) 94.2 + 3 5 144 3 + 4 154 6 + 7 2 114 8 + 6 136 5 + 10 8 6 + 16 2 126 6 9 (no break) 138 3 + 8 7 141 9 + 22 6 127 + 3 2 (no break) Measured on 10 mil compression molded pads heated temperature according to ASTM D-412.
Examples 5, 6 and 7 In these examples porous crosslinkable powders ( 20-25 micron weight average particle size) of ethylene vinyl acetate copolymer containing 5 9 % vinyl acetate and modified with acrylic acid were coated on to glass bottles (preheated to 400 F) and fused in an oven at 400 O F The bottles were subjected to a fragment containment test.
The coated bottle is filled to 95 % full with a dilute solution of sulfuric acid and sodium bicarbonate The bottle, which develops an internal pressure of 60 psig at 70 F, is dropped from four feet onto a bulls eye The weight percent of glass fragments passing a 3 foot diameter circle is determined A good for a total of 4 minutes in a press at the specified coating is one that retains 95 to 100 % of the glass fragments within this circle and has a scatter index less than 2 ounce feet The 20 coatings and results are set out in Table III.
Examples 8-14
In these examples the porous powder compositions contain peroxide and silane.
The adhesion of the coatings applied to 25 glass were evaluated to determine the adhesion of the various coatings to a glass substrate in different environments The test samples were prepared using ethylene vinyl acetate copolymer containing 5 9 percent 30 vinyl acetate and modified with 4 % acrylic acid A solution of 2,5-dimethyl 2,5-di(tTABLE I I
Example
0.5 Elongation 719 + 57 818 + 32 818 + 25 677 + 17 1.0 400 375 325 400 375 325 608 + 17 749 + 68 > 733 535 + 110 438 + 103 > 733 -j Ox F \u O butyl peroxy) hexane to provide 0 2 % peroxide as a crosslinking agent necessary to obtain a tough polymer film, was applied to 20-25 micron polymer powder and several silanes were evaluated at O 1 and 1.0 % concentrations The powder was pressed onto one side of clean glass slides and heated to 375 F ( 190 C) for 3 minutes to provide 4 to 5 mil coatings This left the sides of the coating open to penetration of the various solutions The coated slides were placed into the various solutions.
Failure was determined by examining the coating every hour until the coating could be pulled from the slide without appreciable resistance The slides were aged at room temperature for one week before testing.
The results of the tests are given below in Table IV.
In Figure 2 a glass bottle 2 is shown with a continuous coating of a crosslinked coating 1 made from the powder of the present invention, forming a novel laminate.
The mechanical properties of the peroxide crosslinked resin are not reduced by the presence of the silane A tensile strength of 134 4 + 14 7 kg/cm 2 and an elongation of 353 + 87 percent was obtained on a sample molded at 375 F similar to Example 8 which was molded at the same temperature.
TABLE I I I
Weight Percent Percent Retention of Scatter Index v, nd H Example Peroxide Acid Acetate Mils lass rragments Ounce It O O 5 6 5 9 + 0 9 72 4 16 1 0 0 5 6 8 8 + 1 4 65 4 18 1 6 O 5 O 6 6 6 99 9 0 33 7 O 5 4 0 6 5 5 98 4 1 35 2,5-dimethyl-2,5-di(t-butyl peroxy) hexane.
grafted to 6 percent ethylene vinyl acetate resin.
weight of glass times distance the glass travelled from the bullseye for glass fragments.
Acrylic Vinyl Coating Thickness (‘I ZA L/\ TABLE IV
RESULTS IN HOURS TO FAILURE EX 9 Amino Functional Silane ( 1) 0.1 wt% 1 O wt% EX 10 Amino Functional Silane ( 2) 0.1 wt% 1 O wt% EX 11 Vinyl Functional Silane ( 3) 0.1 wt% 1 O wt% EX 12 Methacrylate Functional Silane ( 4) EX 13 Epoxy Functional Silane ( 5) EX 14 Chloropropyl Functional Silane ( 6) 1.0 N 1 hr 6 hrs 4 hrs 1 hr 1 hr 7 to 20 hr 20 hrs 8 hrs 5 to 7 hrs 5 hrs Na OH (pl H 14) Distilled 1 hr 24 hrs 24 hrs 24 hrs 24 hrs over 400 hrs Water C Distilled 1 hr over 500 hrs Water 23 C ( 1) Dow Corning Z-6020, (CH 30)3 Si(CH 2)3 NHCH 2 CH 2 NH 2 ( 2) Dow Corning Z-6020 ó ( 3) Dow Corning QZ 8-5069, (CH 30)3 Si(CH 2)3 NHCH 2 r CH=CH 2 ( 4) Dow Corning Z-6031 ( 5) Dow Corning Z-6040 (CH 3013 Si (CH 23,0-OCH-CH CH 2 ( 6) Dow Corning Z-6076 (CH 30)3 Si(CH 2)3 C 1 The foregoing comprises a detailed description of a complex invention having many important facets and features It is useful to summarize at this point the major features which form elements of the invention.
The invention is especially preferably utilized with polyethylene, copolymers of polyethylene such as ethylene/vinyl acetate, ethylene/acrylic acid, which copolymers can be either random copolymers or grafted copolymers In addition, the technique is TESTS Solution EX 8 Control No Silane O Un L/i 1,565,674 especially preferably utilized with ionomeric polymers such as those sold by du Pont under the trademark of Surlyn.
These are copolymers of ethylene and methacrylic acid whereby a portion of the acid component in the polymer has been neutralized with a base to form a cationic positively charged derivative of the acid groups such as sodium ion substituents or ammonium ion substituents.
There are several subtle, but important, inter-relationships based on the presence of certain functional monomers in a grafted or random copolymer, if one utilizes it, such as the preferred acrylic acid grafted polyethylene or the preferred methacrylic acid copolymer which has been partially neutralized to form an ionomer.
These relationships constitute important features of the invention and are summarized as follows:
Silane components having a vinyl unsaturated functionality will improve the adhesion to substrates of any polymer in which the vinyl group will be incorporated by the action of the free radical, e g, peroxide initiator In such instances, presence of other functional monomers, such as acrylic acid, is not absolutely necessary for adhesion.
However, if an acrylic acid functionality either grafted or random, or other functionality of similar nature is present in the polymer, then it will be synergistic with the vinyl silane to a large extent and will also be synergistic to a somewhat lesser extent with other silanes having functionality which are capable of reacting with the functionality in the polymer backbone, such as epoxy, amino, etc.
Silanes having a functionality other than vinyl functionality which are incapable of reacting with a polymer containing no functionality, are not capable of imparting improvement to the base polymer When the base polymer has no functionality, the only silane capable of improving the adhesive properties of the coating resulting from the fusion of the powder is a silane having vinyl functionality which will be incorporated into the polymeric backbone via the action of the peroxide.
Silanes containing both vinyl functionality and another functionality capable of interacting with functional substituents in a polymer such as acrylic grafted polyethylene show maximum adhesion synergy and maximum resistance to base hydrolysis synergy It is possible for the vinyl functionality to be incorporated in the backbone through the action of the free radical initiator and it is possible for the non-vinyl functionality in the vinyl silane to interact with the existing functionality in the polymer backbone so that silane monomers are attached to the polymer both through the vinyl functionality and the other nonvinyl functionality in that silane.
A good example of such a silane fitting the last class is Dow Corning QZ 8-5069 which was used in Example 11.
Examples of silanes commercially available that can be used in this invention are listed below.
1 1 1 1 12 1,565,6741 Chemical Name Chemical Formula Vinyltriethoxysilane Vinyl-tris(beta-methoxyethoxy) silane gamma-Methacryloxypropyltrimethoxysilane beta-( 3,4-Epoxycyclohexyl)ethyltrimethoxysilane gamma-Glycidoxypropyltrimethoxysilane gamma-Aminopropyltriethoxysilane N-beta-(Aminoethyl)-gamma-aminopropyltrimethoxysil ane gamma-Chloropropyltrimethoxysilane gamma-Mercaptopropyltrimethoxysilane beta-Mercaptoethyltriethoxysilane It is also to be emphasized that the use of other additives in the porous interstices of each porous particle is contemplated.
Therefore, in addition to peroxides, silanes, it is also contemplated that one or more standard polymer additives can be used.
These include stabilizers, colorants, plasticizers, pigments, finely divided solid fillers, catalysts, foaming agents, antistats, flame retardants, lubricants, etc.
Moreover, a unique application of the porous powder particles of the invention is to utilize them as a carrier medium whereby a concentrate of a particular additive, for instance peroxide, is sorbed on the powder particle.
The activated powder particle is then used as a concentrate to be blended with other powder particles which do not have that additive.
Moreover, the powders of the invention can be beneficially blended with other powders known to be useful for powder coatings such as nylon powder, epoxy powders, vinyl powders, chlorinated polyolefin powders, cellulose acetate butyrate CH 2 2 CH Si(OC 2 Hs)3 CH 2 = CH Si(OCH 2 CHI 2 OCH 3)3 CH 3 O l l CH 2 = C-C-O (CH 2)3 Si (OCH 3)3 O C -H 2 CH 2 Sit OCH 3)3 CH 2 CH-C Hi O(C Ii)3 Si (OCH 3)3 Xo/ NH 2 CH 2 CH 2 CH 2 Si ( O C 2 Hs)3 H NH 2 CHCHN(CH,),SI(OCH) NH 2 CH 2 CH 2 N (CH 2)a Si (OC Ha) 33 CICH 2 CH 2 CH 2 Si (OCH’)3 HSCH 2 CH 2 CH 2 Si (OCH 3) HSCH 2 H 2 Si ( O C 2 Hs)3 powders, polyester powders, acrylic powders, etc.
For instance, a typical blend would comprise 40 to 60 wt % of the porous powder of the invention with:
a) 60-40 % ionomer powder or b) 60-40 % nylon powder or c) 60-40 % epoxy powder Although the powder compositions of the invention are capable of being used per se or mixed with other powders as the sole continuous fused surface coating on substrates, such as glass bottles, they can also be used as a component of a coating system which has two or more different layers.
The coating resulting from the inventive powder compositions can either be that coating adhered directly to the primary substrate or a top coating placed over an already existing coating.
It should be noted that powders such as polyester powders, which are intended to be crosslinked by peroxide free radical cross1,565,674 1,565,674 linking agents, are a particularly suitable combination with the powder compositions of the invention.
Inspection of scanning electron micrographs clearly reveals the porosity of the preferred porous powder particles of this invention The porosity consists of a multiplicity of micro channels indicated by many holes in the surface of each powder particle Such holes have an estimated diameter of 0 5 to 5 microns.
Particle size determinations expressed herein are measured by volume displacement, a well known technique in the art Details can be found in Section VII, Theory of Operation, of the operators manual for the Coulter Counter Model TAIL.
The porous powders of this invention are also suitable for use as carriers for solid inks in electrostatic copiers.
The silane containing powders of this invention are normally applied to a heated substrate If, as in the prior art, a silane is applied separately to a substrate which is then preheated before the powder is applied, vaporization or degradation of the silane or both will likely occur The technique of the invention avoids this disadvantage because the total exposure to heat is minimal.
To reduce the cost of a powder coating the porous powder composition of this invention containing peroxide, polymer and silane may be used as a thin primer coat to adhere to the substrate A top coat formed from the powders described herein except that they require no silane component would then be applied to the primer coat of the powders of this invention Especially preferred topcoats would be crosslinked ethylene/vinyl acetate polymer or polyethylene In addition, nylon is another especially preferred topcoat which does not require crosslinking and would be compatible with the primers described especially if they contain a functional monomer such as acrylic acid or glycidyl acrylate The rationale for utilizing the topcoat is to eliminate the use of silane which is an expensive component yet provide a tough outer layer.

Claims (14)

WHAT WE CLAIM IS:-
I A crosslinkable powder comprising a major amount of porous particles of an organic thermoplastic polymeric material said particles being less than 100 microns in size and said polymeric material having a decomposition temperature higher than ‘C and having sorbed therein a minor amount of an organic peroxide.

2 A crosslinkable composition according to claim I wherein said polymeric material comprises a polyolefin.

3 A crosslinkable composition according to claim 1 or claim 2 wherein said polymeric material comprises a polyolefin modified with an unsaturated organic acid or glycidyl acrylate grafted thereon.

4 A crosslinkable composition according to claim I wherein said polymeric material comprises a random copolymer of unsaturated organic acid and polymerizable olefins.

A crosslinkable composition according to claim 4 wherein said polymer is at least partially neutralized.

6 A crosslinkable composition according to claim I or claim 2 wherein said polyolefin is polyethylene modified with acrylic acid grafted thereon.

7 A crosslinkable composition according to claim 2 wherein said polyolefin is an ethylene-vinyl acetate copolymer modified with acrylic acid grafted thereon.

8 A crosslinkable composition according to any of claims 1 to 7 and an organosilicon compound.

9 A crosslinkable composition according to claim 8 wherein said organosilicon compound contains a vinyl, amine, methacrylate, epoxy or chloropropyl terminal group.

A crosslinkable composition according to claims 8 and 9 containing 99 9 to 96 0 weight % polymeric material, 0 05 to 2.0 weight % 4 organic peroxide and 0 05 to 2.0 weight O organosilicon.

11 A crosslinkable composition according to claims I to 7 comprising from 99.95 to 98 0 weight percent of said polymeric material and from about 0 05 to 2 0 weight percent of said organic peroxide.

12 A crosslinkable composition according to any of the preceding claims wherein said organic peroxide is 2,5dimethyl-2,5-di(t-butyl peroxy) hexane.

13 A crosslinkable composition according to any of claims 2 to 12 wherein said polymer powder is less than 74 microns in particle size.

14 A crosslinkable composition according to claim I substantially as hereinbefore described with particular reference to the accompanying Examples.
A laminate comprising a substrate of glass or metal and a crosslinked polymeric coating attached thereto, prepared by curing a composition according to any of the preceding claims.
K J VERYARD, Suffolk Street, S W 1.
Agent for the Applicants.
Printed for Her Majesty’s Stationery Office by the Courier Press, Leamington Spa, 1980.
Published by the Patent Office, 25 Southampton Buildings, London, WG 2 A l AY, from which copies may be obtained.
1,565,674

GB41932/76A
1975-10-22
1976-10-08
Crosslinkable porous polymer powder and laminate

Expired

GB1565674A
(en)

Applications Claiming Priority (1)

Application Number
Priority Date
Filing Date
Title

US05/624,959

US4225650A
(en)

1975-10-22
1975-10-22
Crosslinkable polymer powder and laminate

Publications (1)

Publication Number
Publication Date

GB1565674A
true

GB1565674A
(en)

1980-04-23

Family
ID=24504031
Family Applications (1)

Application Number
Title
Priority Date
Filing Date

GB41932/76A
Expired

GB1565674A
(en)

1975-10-22
1976-10-08
Crosslinkable porous polymer powder and laminate

Country Status (6)

Country
Link

US
(1)

US4225650A
(en)

JP
(1)

JPS6055546B2
(en)

BE
(1)

BE847499A
(en)

CA
(1)

CA1107889A
(en)

DE
(1)

DE2647700A1
(en)

GB
(1)

GB1565674A
(en)

Cited By (4)

* Cited by examiner, † Cited by third party

Publication number
Priority date
Publication date
Assignee
Title

EP0076709A1
(en)

1981-10-07
1983-04-13
Bridgestone Tire Company Limited
Sandwich glass

US9527967B2
(en)

2012-12-05
2016-12-27
Akzo Nobel Chemicals International B.V.
Peroxide masterbatch based on bioresin

WO2018115767A1
(en)

2016-12-22
2018-06-28
Setup Performance
Powder of spherical crosslinkable polyamide particles, preparation process and use with the selective laser sintering technique

US10316162B2
(en)

2012-12-05
2019-06-11
Akzo Nobel Chemicals International B.V.
Masterbatch comprising a cyclic ketone peroxide

Families Citing this family (51)

* Cited by examiner, † Cited by third party

Publication number
Priority date
Publication date
Assignee
Title

JPS54132631A
(en)

1978-04-07
1979-10-15
Mitsui Petrochem Ind Ltd
Powdered coating composition

US4395459A
(en)

1978-07-11
1983-07-26
Herschdorfer C George
Reinforced laminates produced from crosslinkable thermoplastic olefin polymer material

US4451589A
(en)

1981-06-15
1984-05-29
Kimberly-Clark Corporation
Method of improving processability of polymers and resulting polymer compositions

US4600677A
(en)

1982-03-15
1986-07-15
Xerox Corporation
Organoalkoxysilane carrier coatings

JPS58168666A
(en)

1982-03-31
1983-10-05
Dainippon Ink & Chem Inc
Thermosetting resin composition

US4468492A
(en)

1983-07-15
1984-08-28
Ppg Industries, Inc.
Polymeric organo functional silanes as reactive modifying materials

US4783510A
(en)

1986-06-04
1988-11-08
Taiyo Fishery Co., Ltd.
Process for improving a water absorbent polyacrylic acid polymer and an improved polymer produced by said process

US5009941A
(en)

1987-03-12
1991-04-23
Owens-Corning Fiberglas Corporation
Tube or pipe formed a thermoplastic powder impregnated fiberglass roving

US5024890A
(en)

1987-03-12
1991-06-18
Owens-Corning Fiberglass Corporation
Size composition for impregnating filament strands and glass fibers coated therein

US5026410A
(en)

1987-03-12
1991-06-25
Owens-Corning Fiberglas Corporation
Process for impregnating filament strands

US4888394A
(en)

1988-06-15
1989-12-19
Phillips Petroleum Company
Process to graft stereoregular polymers of branched, higher alpha-olefins and compositions thereof

DE3924679A1
(en)

1989-07-26
1991-01-31
Bayer Ag

USE OF POLYURETHANES CONTAINING (METH) ACRYLOYL GROUPS AS BINDERS FOR POWDER COATINGS

IL103705A
(en)

1991-11-15
1995-12-08
Kuehnle Manfred R
Electrothermal printing ink and method and apparatus for electronic printing therewith

JP2792324B2
(en)

1992-04-30
1998-09-03
日本鋼管株式会社

Multi-layer galvanized steel sheet

US6399708B2
(en)

1993-07-19
2002-06-04
Visteon Systemes Interieurs S.A.S.
Grafted and crosslinkable pulverulent thermoplastic polyolefin composition which has elasticity and flexibility properties

JP3703487B2
(en)

1994-04-11
2005-10-05
宇部日東化成株式会社

Crosslinked resin-coated silica fine particles and method for producing the same

US5929129A
(en)

1994-09-19
1999-07-27
Sentinel Products Corp.
Crosslinked foamable compositions of silane-grafted, essentially linear polyolefins blended with polypropylene

US5932659A
(en)

1994-09-19
1999-08-03
Sentinel Products Corp.
Polymer blend

US5883144A
(en)

1994-09-19
1999-03-16
Sentinel Products Corp.
Silane-grafted materials for solid and foam applications

EP0702032B1
(en)

1994-09-19
2002-11-27
Sentinel Products Corp.
Cross-linked foam structures of essentially linear polyolefines and process for manufacture

MX9504934A
(en)

1994-12-12
1997-01-31
Morton Int Inc
Smooth thin film powder coatings.

US5891553A
(en)

1995-12-21
1999-04-06
Clark-Schwebel, Inc.
Crosslinkable polymeric coatings and films and composite structures incorporating same

US6395839B2
(en)

1996-04-01
2002-05-28
Visteon Systemes Interieurs S.A.S.
Grafted and crosslinkable pulverulent thermoplastic polyolefin composition which has elasticity and flexibility properties

US5844009A
(en)

1996-04-26
1998-12-01
Sentinel Products Corp.
Cross-linked low-density polymer foam

CA2203595A1
(en)

1996-04-26
1997-10-26
Robert F. Hurley
Cross-linked polyolefin tape

US5882776A
(en)

1996-07-09
1999-03-16
Sentinel Products Corp.
Laminated foam structures with enhanced properties

US5876813A
(en)

1996-07-09
1999-03-02
Senitnel Products Corp
Laminated foam structures with enhanced properties

US5938878A
(en)

1996-08-16
1999-08-17
Sentinel Products Corp.
Polymer structures with enhanced properties

US6221928B1
(en)

1996-11-15
2001-04-24
Sentinel Products Corp.
Polymer articles including maleic anhydride

US6255386B1
(en)

1996-12-31
2001-07-03
Kimberly-Clark Worldwide, Inc.
Blends of polyolefin and poly(ethylene oxide) and process for making the blends

US6063866A
(en)

1996-12-31
2000-05-16
Kimberly-Clark Worldwide, Inc.
Blends of polyolefin and poly(ethylene oxide) and process for making the blends

US5912076A
(en)

1996-12-31
1999-06-15
Kimberly-Clark Worldwide, Inc.
Blends of polyethylene and peo having inverse phase morphology and method of making the blends

US5976694A
(en)

1997-10-03
1999-11-02
Kimberly-Clark Worldwide, Inc.
Water-sensitive compositions for improved processability

US6117947A
(en)

1997-12-31
2000-09-12
Kimberly-Clark Worldwide, Inc.
Method of modifying poly(ethylene oxide)

US6372850B2
(en)

1997-12-31
2002-04-16
Kimberly-Clark Worldwide, Inc.
Melt processable poly (ethylene oxide) fibers

US6350518B1
(en)

1998-06-01
2002-02-26
Kimberly-Clark Worldwide, Inc.
Methods of making blend compositions of an unmodified poly vinyl alcohol and a thermoplastic elastomer

AU2377700A
(en)

1998-12-29
2000-07-31
Kimberly-Clark Worldwide, Inc.
Heat-activated adhesives

DE19908018A1
(en)

1999-02-25
2000-08-31
Basf Coatings Ag

Powder slurry curable thermally and with actinic radiation, process for their preparation and their use

DE19908013A1
(en)

1999-02-25
2000-08-31
Basf Coatings Ag

With actinic radiation and optionally curable powder slurries, process for their preparation and their use

US6576576B1
(en)

1999-12-29
2003-06-10
Kimberly-Clark Worldwide, Inc.
Multicomponent fibers

US6610793B1
(en)

2000-05-26
2003-08-26
Kimberly-Clark Worldwide, Inc.
Modified poly(ethylene oxide), method of making same and articles using same

US6790519B1
(en)

2000-05-26
2004-09-14
Kimberly-Clark Worldwide, Inc.
Moisture-induced poly(ethylene oxide) gel, method of making same and articles using same

US6607819B2
(en)

2000-12-28
2003-08-19
Kimberly-Clark Worldwide, Inc.
Polymer/dispersed modifier compositions

US6403706B1
(en)

2000-12-28
2002-06-11
Kimberly-Clark Worldwide, Inc.
Methods of making polymer/dispersed modifier compositions

US6515075B1
(en)

2001-07-12
2003-02-04
Kimberly-Clark Worldwide, Inc.
Films, fibers and articles of chemically modified polyethylene oxide compositions with improved environmental stability and method of making same

EG23499A
(en)

2002-07-03
2006-01-17
Advanced Plastics Technologies
Dip, spray, and flow coating process for forming coated articles

US7204901B2
(en)

2003-02-03
2007-04-17
Zicron Corporation
Low cost process for manufacture of hurricane resistant, glass, impact resistant units

EP2154186B1
(en)

2007-05-21
2019-09-18
Kuraray Co., Ltd.
Crosslinkable polyvinyl acetal porous powder, method for producing the same, and use of the same

MY178296A
(en)

2012-12-05
2020-10-07
Akzo Nobel Chemicals Int Bv
Peroxide masterbatch based on bioresin

CN112898875A
(en)

2021-03-04
2021-06-04
苏州群鹰防腐材料有限公司
High-performance ozone-resistant environment-friendly anticorrosive paint and preparation method thereof

CN115595021B
(en)

2022-11-09
2023-11-21
北京化工大学
Hot-dip-molding powder fireproof coating and preparation method and application thereof

Family Cites Families (7)

* Cited by examiner, † Cited by third party

Publication number
Priority date
Publication date
Assignee
Title

CA704812A
(en)

1965-03-02
L. Kelso Robert
Polyester, polyglycidyl acrylate and organosilicon composition

US2859202A
(en)

1957-04-10
1958-11-04
Gen Electric
Siloxane comprising 2, 5-dimethyl-2, 5-dihydroperoxy hexane

BE757247A
(en)

1969-10-09
1971-04-08
Union Carbide Corp

THERMOPLASTIC POLYMERS LOADED WITH MINERAL OXIDE PARTICLES

US3699186A
(en)

1971-03-30
1972-10-17
Dart Ind Inc
Polyolefins modified with unsaturated glycidyl compounds and polyacrylate compounds

US3804919A
(en)

1972-04-20
1974-04-16
Dart Ind Inc
Synergistic blends of modified polyolefins and unmodified polyolefins

US3903339A
(en)

1973-05-25
1975-09-02
Liberty Glass Co
Glass container coated with plastic containment film and method of making

US3919143A
(en)

1974-02-04
1975-11-11
Goodrich Co B F
Vulcanizable compositions containing halogen-bearing elastomeric polymers

1975

1975-10-22
US
US05/624,959
patent/US4225650A/en
not_active
Expired – Lifetime

1976

1976-10-08
GB
GB41932/76A
patent/GB1565674A/en
not_active
Expired

1976-10-18
CA
CA263,601A
patent/CA1107889A/en
not_active
Expired

1976-10-21
JP
JP51125590A
patent/JPS6055546B2/en
not_active
Expired

1976-10-21
BE
BE171681A
patent/BE847499A/en
not_active
IP Right Cessation

1976-10-21
DE
DE19762647700
patent/DE2647700A1/en
not_active
Ceased

Cited By (5)

* Cited by examiner, † Cited by third party

Publication number
Priority date
Publication date
Assignee
Title

EP0076709A1
(en)

1981-10-07
1983-04-13
Bridgestone Tire Company Limited
Sandwich glass

US9527967B2
(en)

2012-12-05
2016-12-27
Akzo Nobel Chemicals International B.V.
Peroxide masterbatch based on bioresin

US10316162B2
(en)

2012-12-05
2019-06-11
Akzo Nobel Chemicals International B.V.
Masterbatch comprising a cyclic ketone peroxide

WO2018115767A1
(en)

2016-12-22
2018-06-28
Setup Performance
Powder of spherical crosslinkable polyamide particles, preparation process and use with the selective laser sintering technique

US11236242B2
(en)

2016-12-22
2022-02-01
SETUP Performance SAS
Powder of spherical crosslinkable polyamide particles, preparation process and use with the selective laser sintering technique

Also Published As

Publication number
Publication date

JPS6055546B2
(en)

1985-12-05

US4225650A
(en)

1980-09-30

CA1107889A
(en)

1981-08-25

JPS5251437A
(en)

1977-04-25

BE847499A
(en)

1977-04-21

DE2647700A1
(en)

1977-04-28

Contact information