WO2020229416A1 - Mousses de pvc - Google Patents

Mousses de pvc Download PDF

Info

Publication number
WO2020229416A1
WO2020229416A1 PCT/EP2020/063062 EP2020063062W WO2020229416A1 WO 2020229416 A1 WO2020229416 A1 WO 2020229416A1 EP 2020063062 W EP2020063062 W EP 2020063062W WO 2020229416 A1 WO2020229416 A1 WO 2020229416A1
Authority
WO
WIPO (PCT)
Prior art keywords
colloidal silica
pvc
silica
plasticisers
organosilane
Prior art date
Application number
PCT/EP2020/063062
Other languages
English (en)
Inventor
Asbjorn HOLT
Harald Jacobsen
Hans Lagnemo
Per Restorp
Anders Torncrona
Original Assignee
Nouryon Chemicals International B.V.
Inovyn Europe Limited
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.)
Filing date
Publication date
Application filed by Nouryon Chemicals International B.V., Inovyn Europe Limited filed Critical Nouryon Chemicals International B.V.
Publication of WO2020229416A1 publication Critical patent/WO2020229416A1/fr

Links

Classifications

    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/009—Use of pretreated compounding ingredients
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0023—Use of organic additives containing oxygen
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066—Use of inorganic compounding ingredients
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/102—Azo-compounds
    • C08J9/103—Azodicarbonamide
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/30—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by mixing gases into liquid compositions or plastisols, e.g. frothing with air
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
    • 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
    • C08J2327/00—Characterised by the use of 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; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of 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; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04—Characterised by the use of 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; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2327/06—Homopolymers or copolymers of vinyl chloride

Definitions

  • the present invention relates to PVC foams which incorporate silica particles which are derived from colloidal silica.
  • the invention also relates to a method in which such foams can be produced, and further relates to the use of colloidal silica in producing PVC foams, in particular reducing the foam density.
  • PVC polyvinyl styrene-co-styrene-co-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-S-SSS-SSS-SSS-SSS-SSS-SSS-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-
  • PVC can be produced in the form of foams, which find use in applications such as floor coverings and carpet backing, textured wallpaper, furniture cushioning and padding and also in gaskets, filters, cleaning sponges and insulation.
  • a process for making PVC foams is described, for example, in US3708441.
  • PVC nanocomposites can be prepared in order to modify various properties of the polymer.
  • EP 2 428 531 describes the production of PVC modified with a nanomaterial source, which can be selected from silica, montmorillonite, organically modified montmorillonite, nano-metal, metal oxides, or inorganic or organic fibres.
  • WO 2015/007522 also describes the preparation of nanoparticle-modified polymers, such as PVC, in which the use of colloidal silica is exemplified.
  • these documents do not relate to PVC foams.
  • the invention is directed to a PVC foam comprising silica particles derived from a colloidal silica.
  • the invention is also directed to a plastisol capable of forming a PVC foam comprising a dried mixture of PVC and colloidal silica, a plasticiser and a blowing agent.
  • the invention is additionally directed to making such a foam, by mixing a PVC dispersion or emulsion with colloidal silica, drying the mixture of PVC and colloidal silica to form a dried PVC-colloidal silica mixture, forming a plastisol by adding a plasticiser and a blowing agent to the dried PVC-colloidal silica mixture, and heating the plastisol to a temperature sufficient to cause formation of a foam.
  • the invention is further directed to the use of colloidal silica in reducing the density of PVC foams.
  • Figure l is a graph of viscosity versus shear rate for silica-free and silica-containing PVC plastisols.
  • Figure 2 is a bar chart showing foam densities for silica-free and silica-containing PVC foams of Examples 1 to 6.
  • Figure 3 is a bar chart showing foam densities for silica-free and silica-containing PVC foams of Examples 7 to 13.
  • Figure 4 is a bar chart showing relative expansion of the silica-free and silica-containing PVC foams of Examples 1 to 6.
  • Figure 5 is a bar chart showing relative expansion of the silica-free and silica-containing PVC foams of Examples 7 to 13.
  • Figure 6 is a bar chart showing relative expansion of the silica-free and silica-containing PVC foams of Examples 14 to 20.
  • Figure 7 is a bar chart showing the yellowing index of Examples 1 to 6 after foam formation.
  • Figure 8 is a bar chart showing the yellowing index of Examples 7 to 13 after foam formation.
  • Figure 9 is a series of photographs of the foams of Examples 14 to 20.
  • the present invention is directed to PVC foams which have improved properties, in particular a reduced density without loss of expansion capability. This is achieved by incorporating colloidal silica, and in embodiments organosilane-modified colloidal silica, into the foam. Not only is reduced foam density achieved, but also there is no significant loss of expansion of the foam or any significant reduction in thermal stability. In many cases, the expansion characteristics and the thermal stability are improved.
  • the term“colloidal silica” refers to a dispersion comprising 1 to 50wt% silica particles dispersed in an aqueous medium.
  • the aqueous medium may comprise organic solvent, but where it does so it preferably comprises less than 10wt% organic solvent. If dissolved organic solvent is present, the aqueous medium more preferably contains no more than 5 wt% organic solvent.
  • Typical organic solvents when present are water- miscible, for example being selected from one or more of C1-4 alkyl alcohols, C1-4 aldehydes, C1-4 ketones, C1-4 carboxylic acids and their C1-4 alkyl esters.
  • Aqueous silica sols can be basic, having a pH in the range of from 8.0 to 12.0, for example from 8.0 to 11, or from 9.0 to 11.0.
  • Other components of such sols include the presence of alkali metals, typically one or more of lithium, sodium and potassium. Typically sodium is the sole or predominant alkali metal.
  • the alkali metals can be derived from soluble silicate solutions (e.g. water glass) that can be used to make the colloidal silica using conventional processes.
  • aqueous alkali metal silicates or water glass examples include lithium, sodium and potassium silicates, preferably sodium silicate.
  • the silica particles are typically amorphous nanoparticles, and most typically have a particle diameter ranging from 2 to 150 nm as discussed further below.
  • the colloidal silica is made from particle growth from a soluble silicate or a polysilicic acid solution, and is not prepared by creating a dispersion from a solid form of silica nanoparticle.
  • the colloidal silica is preferably not derived from solid, amorphous forms of silica such as fumed silica, silica fume and precipitated silica. This is because, in general, solid forms of silica nanoparticle tend to be in the form of agglomerates of the primary nanoparticles, and it is not possible to disperse such silicas to create a colloidal silica comprising predominantly the discrete primary particles because larger agglomerates tend to remain.
  • colloidal silicas made from particle growth from a soluble silicate or a polysilicic acid solution do not include such large silica agglomerates. They are therefore stable and do not noticeably gel or precipitate for many months, typically for greater than 12 months. It is also preferred that the colloidal silica is not derived from crystalline forms of silica, such as micro-quartz or nano-quartz, which suffer the additional disadvantage of potential health risks.
  • the colloidal silica is made by increasing the pH of a polysilicic acid solution (with a pH typically in the range of from 1-3) to a pH value of 7 or more, typically 8 to 12, for example 9 to 11. This is usually achieved using a basic alkali metal salt solution, such as alkali metal hydroxide or alkali metal silicate.
  • the polysilicic acid can be prepared from a soluble silicate source, e.g. an alkali metal silicate, such as sodium silicate. This can be achieved by ion-exchange or treatment with an acid.
  • the content of alkali metals in the starting silica sol is typically in the range of from 0.1 to 5.0 wt%, expressed as alkali metal oxide. In embodiments, it is from 0.2 to 3.0 wt%.
  • the silica concentration in the colloidal silica is preferably from 2 to 40wt% or from 3 to 35wt%. As used herein, silica concentrations are expressed as SiCk. A preferred minimum concentration is 5wt%, and most preferred ranges are therefore 5 to 50wt%, and more preferably 5 to 40wt% or 5 to 35wt%.
  • the colloidal silica particles typically have a surface area in the range of from 50 to 1000 m 2 g 1 , for example in the range of from 100 to 700 m 2 g 1 , such as from 140 to 550 m 2 g 1 .
  • the surface area of colloidal silica particles in a silica sol can be calculated from NaOH titration following the method of Sears (Sears; Anal. Chem., 1956, 28(12), 1981-1983).
  • the colloidal silica particles typically have a particle diameter ranging from 2 to 150 nm, for example from 2 to 100 nm, or from 3 to 75 nm. In further embodiments, the particle diameter is in the range of from 4 to 50 nm.
  • the particle diameters can be calculated from the titrated surface area using a method described in "The Chemistry of Silica", by Iler, K. Ralph, page 465, John Wiley & Sons (1979). Based on the assumption that the silica particles have a density of 2.2 g cm 3 , and that all particles are of the same size, have a smooth surface area and are spherical, then the particle diameter can be calculated from Equation 1 :
  • the S value is in the range of from 20 to 95 %, for example from 30 to 90%.
  • the S-value is measured and calculated as described by Iler & Dalton (Iler & Dalton; J. Phys. Chem. 60(1956), 955-957).
  • the S-value indicates the degree of aggregate or microgel formation. A lower S-value is indicative of a higher degree of aggregation.
  • the density of the silica sol is at least in part dependent on the silica content, and is typically in the range of from 1.01 to 1.45 g cm 3 , and preferably of from 1.01 to 1.20 g cm 3 . Density can be determined using ASTM D4052-18a.
  • the viscosity of the starting aqueous silica sol is typically less than 40 cP, for example less than 30 cP, and in particular less than 20 cP. In embodiments, it is less than 10 cP. In further embodiments, the viscosity is 1 cP or more. These viscosities are measured at 20.0°C. Viscosities of silica sols, including those described herein, can be measured using a conventional rotational viscometer. A method that can be used is ASTM D4016-14.
  • the colloidal silica particles can be dispersed in the presence of stabilising cations, which can be selected from alkali metals (e.g. K + , Na + , Li + ), NEL 1 , and organic cations (such as quaternary amines, tertiary amines, secondary amines, and primary amines), and mixtures thereof.
  • stabilising cations can be selected from alkali metals (e.g. K + , Na + , Li + ), NEL 1 , and organic cations (such as quaternary amines, tertiary amines, secondary amines, and primary amines), and mixtures thereof.
  • the colloidal silica in embodiments can be functionalised with organosilane groups, which in embodiments are hydrophilic organosilane moieties.
  • Organosilane-functionalised colloidal silica can be made by conventional processes, as described for example in W02004/035473 or W02004/035474, and comprises colloidal silica particles modified with an organosilane moiety, which in embodiments is a hydrophilic organosilane moiety.
  • the organosilane-functionalised colloidal silica is formed from a reaction between one or more organosilane reactants, which can be expressed generally by the formula A4- y Si-[R m ] y , and one or more silanol groups on the silica surface, i.e. [SiC j-OH groups.
  • organosilane reactants which can be expressed generally by the formula A4- y Si-[R m ] y
  • silanol groups on the silica surface i.e. [SiC j-OH groups.
  • each“A” is typically independently selected from Ci- 6 alkoxy, Ci- 6 haloalkoxy, hydroxy and halide.
  • Other options are the use of siloxanes, e.g. of formula [R m ]bA3-bSi ⁇ -0-SiA2- c [R m ]c ⁇ a-0-SiA3-b[R m ]b, where a is 0 or an integer of 1 or more, typically from 0 to 5; b is from 1 to 3; and c is from 1 to 2.
  • disilazanes of formula ⁇ [R m ] b A3- b Si ⁇ 2-NH where b is from 1 to 3.
  • fluoro and chloro are preferred halo substituents.
  • the organosilane reactant can undergo a prehydrolysis step, in which one or more“A” groups are converted to -OH, as described for example by Greenwood and Gevert, Pigment and Resin Technology, 201 1, 40(5), pp 275-284.
  • the organosilane reactant can react with a surface silanol group to form from one to three Si-O-Si links between the silica surface and the organosilane silicon atom, i.e.
  • organosilane it is also possible for at least a portion of the organosilane to be in a dimeric form or even oligomeric form before binding to the colloidal silica, i.e. where the two or more organosilane moieties are bound to each other through Si-O-Si bonds.
  • the chemically bound organosilane groups can be represented by the formula [ ⁇ S1O2 ⁇ - 0-] 4-y-z- Si[D] z [R m ] y .
  • the group (SiCkj-O- represents an oxygen atom on the silica surface.
  • the organosilane silicon atom has at least one, and optionally up to three such bonds to the silica surface, where 4-y-z is from 1 to 3, and usually in the range of from 1 to 2, i.e. 4-y-z is at least 1, and no more than 3.
  • Group“D” is optionally present, and z is in the range of from 0 to 2.
  • the organosilane silicon atom has from 1 to 3 [R m ] groups, i.e. y is from 1 to 3, typically from 1 to 2. Where there is more than 1 R m group, they can be the same or different.
  • the organosilane silicon contains unreacted“A” groups, and/or contains hydroxyl groups where the“A” group has been removed, for example through a hydrolysis reaction.
  • an Si-O-Si link can be formed with the silicon atom of a neighbouring organosilane group.
  • group“D” can (on each occurrence) be selected from the groups defined under“A” above, and also from hydroxy groups and -O- [SiR m ]’ groups where the
  • [SiR m ]’ group is a neighbouring organosilane group.
  • R m is an organic moiety directly bound to a silicon atom by a direct Si-C bond.
  • the silane moiety attached to the silica surface can be represented by oSiR m .
  • R m can comprise from 1 to 16 carbon atoms, for example from 1 to 12 carbon atoms, or from 1 to 8 carbon atoms.
  • each R m can be the same or different.
  • R m is in embodiments a hydrophilic moiety.
  • the hydrophilic moiety enables the modified colloidal silica to be miscible with the aqueous phase.
  • hydrophilic moieties are preferred, as they tend to impart better dirt pick-up resistance compared to hydrophobic moieties.
  • R m comprises at least one group selected from hydroxyl, thiol, carboxyl, ester, epoxy, acyloxy, ketone, aldehyde, (meth)acryloxy, amino, amido, ureido, isocyanate or isocyanurate.
  • hydrophilic moieties comprise at least one heteroatom selected from O and N, and comprise no more than three consecutive alkylene (-CH2-) groups linked together.
  • R m comprises no aldehyde groups.
  • R m can comprise alkyl, alkenyl, epoxy alkyl, aryl, heteroaryl, Ci- 6 alkylaryl and Ci- 6 alkylheteroaryl groups, optionally substituted with one or more groups selected from ER n .
  • E is either not present, or is a linking group selected from -0-, -S-,
  • R n is linked to E, or directly to R m if E is not present, and is selected from halogen (typically F, Cl or Br), alkyl, alkenyl, aryl, heteroaryl, C 1-3 alkylaryl and C 1-3
  • alkylheteroaryl R n can optionally be substituted with one or more groups selected from hydroxyl, halogen (typically F, Cl or Br), epoxy ,-OR p or -N(R P )2 where each R p is as defined above. If E is present, R n can also be hydrogen.
  • alkyl and alkenyl groups can be aliphatic, cyclic or can comprise both aliphatic and cyclic portions. Aliphatic groups or portions can be linear or branched. Where any group or substituent comprises halogen, the halogen is preferably selected from F, Cl and Br.
  • groups can undergo hydrolysis reactions under conditions experienced in the colloidal silica medium.
  • groups containing moieties such as halide, acyloxy, (meth)acryloxy and epoxy groups can hydrolyse to form corresponding carboxyl, hydroxyl or glycol moieties.
  • one or more R m groups are Ci- 8 alkyl, Ci- 8 haloalkyl, Ci- 8 alkenyl or Ci- 8 haloalkenyl, typically Ci- 8 alkyl or Ci- 8 alkenyl, with an optional halide (e.g. chloride) substituent. Examples include methyl, ethyl, chloropropyl, isobutyl, cyclohexyl, octyl and phenyl.
  • These Ci- 8 groups can, in embodiments, be Ci- 6 groups or, in further
  • C 1-4 groups Longer carbon chains tend to be less soluble in an aqueous system, which makes synthesis of the organosilane-modified colloidal silica more complex.
  • R m is a group comprising from 1 to 8 carbon atoms, e.g. a Ci- 8 alkyl group, and which additionally comprises an ER n substituent where E is oxygen and R n is selected from optionally substituted Ci- 8 -epoxyalkyl and Ci- 8 hydroxyalkyl.
  • R n can be optionally substituted alkylisocyanurate. Examples of such ER n substituents include 3-glycidoxypropyl and 2,3-dihydroxypropoxypropyl.
  • R m is a group comprising from 1 to 8 carbon atoms, e.g. a Ci- 8 alkyl group, and which additionally comprises an ER n substituent where E is not present, and R n is epoxyalkyl, for example an epoxy cycloalkyl.
  • R m group is beta- (3, 4-epoxy cy cl ohexyl)ethyl.
  • the epoxy group can alternatively be two neighbouring hydroxyl groups, e.g. R n can be a dihydroxyalkyl such as a dihydroxy cycloalkyl, and R m being (3,4-dihydroxycyclohexyl)ethyl.
  • organosilane-modified silica is produced by reacting a mixture of two or more organosilanes with colloidal silica, or by mixing two or more separately prepared organosilane-modified colloidal silicas.
  • the colloidal silica can be modified by more than one organosilane moiety.
  • the additional organosilane moieties do not necessarily themselves have to be hydrophilic in nature.
  • they can be hydrophobic silanes, such as Ci-20 alkyl or alkenyl silane, for example Ci- 8 alkyl or alkenyl silane.
  • the resulting modified colloidal silica should still be miscible with the aqueous phase.
  • the organosilane or at least one organosilane comprises epoxy groups, for example as found in epoxyalkyl silanes or epoxyalkyloxyalkyl silanes.
  • the organosilane can comprise a hydroxyl-substituent group, for example selected from hydroxyalkyl and hydroxyalkyloxyalkyl groups comprising one or more hydroxyl groups, e.g. 1 or 2 hydroxyl groups. Examples include organosilanes containing a glycidoxy, glycidoxypropyl, dihydropropoxy or dihydropropoxypropyl group.
  • epoxy groups can hydrolyse to form corresponding vicinal diol groups. Therefore, the invention also encompasses the diol equivalents of the above epoxy group-containing compounds.
  • the silane compounds can form stable covalent siloxane bonds (Si-O-Si) with the silanol groups.
  • they can be linked to the silanol groups, e.g. by hydrogen bonds, on the surface of the colloidal silica particles. It is possible that not all silica particles become modified by organosilane.
  • the proportion of colloidal silica particles that become functionalised with organosilane will depend on a variety of factors, for example the size of the silica particles and the available surface area, the relative amounts of organosilane reactant to colloidal silica used to functionalise the colloidal silica, the type of organosilane reactants used and the reaction conditions.
  • the degree of modification (DM) of silica surface by organosilane can be expressed according to the following calculation (Equation 2), in terms of the number of silane molecules per square nanometre of silica surface:
  • DM is the degree of surface modification in units of nm 2 ;
  • A is Avogadro’s constant
  • N organosiiane is the number of moles of organosilane reactant used
  • S siiica is the surface area of the silica in the colloidal silica, in m 2 g 1 ;
  • Msiiica is the mass of silica in the colloidal silica, in g.
  • DM can be at least 0.5 molecules of silane per nm 2 , and is preferably in the range of from 0.5 to 4.0 molecules per nm 2 .
  • Preferred embodiments have DM in the range of from 0.5 to 3.0, for example from 0.8 to 2.2 molecules per nm 2 .
  • the surface area of the silica is conveniently measured by Sears titration (Sears; Anal. Chem., 1956, 28(12), 1981-1983).
  • the colloidal silica used in the composition of the present invention is a stable colloid.
  • stable is meant that the organosilane-functionalised colloidal silica particles dispersed in the aqueous medium do not substantially gel or precipitate within a period of at least 2 months, and preferably at least 4 months, more preferably at least 5 months at normal storage at room temperature (20°C).
  • the relative increase in viscosity of the silane-functionalised colloidal silica dispersion between its preparation and up to two months after preparation is lower than 100%, more preferably lower than 50%, and most preferably lower than 20%.
  • the relative increase in viscosity of the silane-functionalised colloidal silica between its preparation and up to four months after preparation is lower than 200%, more preferably lower than 100%, and most preferably lower than 40%.
  • PVC refers to vinyl chloride polymers, and also copolymers.
  • PVC polymer
  • polymer mean a polymer containing at least 50% by weight, preferably at least 60% by weight, particularly preferably at least 70% by weight and particularly preferably at least 85% by weight of monomeric units derived from vinyl chloride (monomer), i.e. both homopolymers of vinyl chloride (containing 100% by weight of monomers derived from vinyl chloride) and vinyl chloride copolymers with one or more ethylenically unsaturated monomers.
  • ethylenically unsaturated monomers copolymerizable with vinyl chloride include chlorinated monomers such as vinylidene chloride, fluorinated monomers such as vinylidene fluoride, monomers containing both chlorine and fluorine such as
  • chlorotrifluoroethylene vinyl esters such as vinyl acetate, vinyl ethers such as vinyl methyl ether, dialkyl maleates such as dibutylmaleate, (meth) acrylic monomers such as n-butyl acrylate and methyl methacrylate, styrenic monomers such as styrene, and olefmic monomers such as ethylene, propylene and butadiene.
  • vinyl esters such as vinyl acetate
  • vinyl ethers such as vinyl methyl ether
  • dialkyl maleates such as dibutylmaleate
  • (meth) acrylic monomers such as n-butyl acrylate and methyl methacrylate
  • styrenic monomers such as styrene
  • olefmic monomers such as ethylene, propylene and butadiene.
  • PVC may be prepared by suspension polymerisation of vinyl chloride in a suspending liquid and in the presence of a suspending agent. This produces a slurry (or suspension) of PVC particles, typically of the order of 100 to 200 microns particle size. The resulting slurry of PVC is then dried, usually by centrifuging followed by fluid bed drying, to give a porous (i.e. sorbent) PVC.
  • PVC produced by the suspension method is referred to as“S-PVC”.
  • S- PVC can absorb plasticisers to give a dry blend.
  • PVC can also be produced by what are generally known as paste polymerisation processes. These are so-called because the resin formed, which may also be referred to as paste-PVC, is non-absorbent at ambient temperatures, so that when mixed with a plasticizer a paste (or plastisol) is formed. As well as the difference in porosity of the formed PVC compared to S-PVC, paste processes may also be characterised in that the polymerisation produces a latex of polymer particles of relatively small size compared to the S-PVC process, typically 0.2 to 5 microns. The latex can be dried, for example by spray-drying, to produce PVC particles in the form of agglomerates. As well as being non-absorbent at ambient temperatures, the dried PVC polymer particles are compact and also much smaller than the dried particles produced by the suspension PVC processes.
  • paste polymerisation processes are so-called because the resin formed, which may also be referred to as paste-PVC, is non-absorbent at ambient temperatures, so that when mixed
  • An example of such a process is an emulsion polymerisation process.
  • an emulsifier is used to produce small droplets of the monomer in a liquid phase.
  • the latex may then be spray-dried to produce PVC particles in the form of agglomerates, typically with a particle size of up to 63 microns.
  • the PVC formed by emulsion polymerisation is a type of paste-PVC and may be referred to as such, but more specifically is usually referred to as“E-PVC”.
  • paste PVC processes include those known as mini-emulsion and micro-suspension, which polymerisations produce latexes of polymer particles typically of the order of about 0.2 to 5 microns particle size. These latexes can also be spray-dried to produce paste PVC particles.
  • Resin particles produced by paste polymerisation are generally used to make sheets and plastisols.
  • the PVC in the method of the present invention is most preferably a paste-PVC or ⁇ - PVC”.
  • the PVC can be provided in the form of a dispersion, which in embodiments is an aqueous dispersion.
  • PVC dispersion refers to particles of PVC dispersed in a continuous phase, i.e. a liquid phase, which in embodiments is water.
  • Aqueous dispersions can comprise other solvents or liquids that are soluble or miscible with water, which in embodiments are present in amounts of from 0 to 10wt%, for example from 0 to 5wt%.
  • the PVC dispersion can be prepared by any suitable technique.
  • the PVC dispersion is preferably a latex prepared using procedures similar to those described in
  • the PVC dispersion is formed by paste polymerisation, comprising the steps of: a) forming an emulsion comprising vinyl chloride monomer, and optionally one or more comonomers, in an aqueous material; and
  • the method of the present invention can comprise the steps of: a) forming an emulsion comprising vinyl chloride monomer, and optionally one or more comonomers, in an aqueous material
  • paste polymerisation is a polymerisation which produces a latex comprising particles of polymer, which latex when spray-dried produces PVC which is non-absorbent at ambient temperatures, so that when mixed with a plasticizer a paste (or plastisol) is formed.
  • a "latex" is a dispersion of polymer particles in a liquid, said particles having a volume average particle size as measured by light scattering of from 0.01 to 8 microns, and more preferably from 0.2 to 5 microns.
  • the paste polymerisation is preferably an emulsion polymerisation where the latex preferably comprises particles of polymer of size from 0.2 to 3 microns, such as particles of polymer of size from 0.2 to 1 micron.
  • Vinyl chloride monomer may be used as the only monomer, in which case the polymer formed in step (b) is PVC homopolymer.
  • one or more co-monomers may be included, such as vinyl acetate, in which case the polymer formed in step (b) is a PVC copolymer.
  • the term "polymer” encompasses both homopolymers and copolymers.
  • the polymer formed in this aspect preferably has a glass transition temperature above 65°C.
  • the glass transition temperature is above 66°C. such as at least 68°C, and most preferably at least 70°C, such as 70-85°C.
  • the glass transition temperature should be measured on the polymer without addition of the colloidal silica. It may be determined by separating and spray drying a portion of the latex prior to addition of the source of the colloidal silica. The glass transition temperature should be determined by differential thermal analysis according to the method of ISO 1 1357-2, Plastics- Differential Scanning Calorimetry - Part 2:
  • the emulsion of step (a) is generally an oil in water emulsion in which droplets of the monomer or monomers are dispersed in an aqueous continuous phase.
  • the colloidal silica is incorporated into the PVC by mixing a PVC dispersion with the colloidal silica or modified colloidal silica.
  • a convenient way of achieving this is by adding the aqueous colloidal silica to the PVC dispersion.
  • the mixture can be stirred to achieve good homogeneity and incorporation.
  • PVC/silica mixture is typically in the range of from 0.1 to 10 phr (parts per hundred resin), on a dry basis. In embodiments, the range is from 0.2 to 7 phr, and in further embodiments 0.3 to 5 phr. In embodiments, the range is 0.5 to 4 phr.
  • (1 phr means 1 weight part of (modified) colloidal silica in 100 weight parts of PVC, based on dry weight (and giving a total of 101 parts of modified PVC), whilst 10 phr means 10 weight parts of (modified) colloidal silica to 100 weight parts of PVC based on dry weight (and giving a total of 110 parts of modified PVC).
  • the amount of colloidal silica or organosilane-modified colloidal silica particles in the PVC is in the range of from 0.1 to 9wt%. In embodiments, the amount is in the range of from 0.2 to 7wt%, for example 0.3 to 5wt% or 0.5 to 4wt%.
  • the PVC/colloidal silica mixture is then dried, for example using a rotary disk dryer or a spray dryer.
  • the spray-dried particles may have a volume average particle size in the range of from 0.1 to 100 microns, for example from 1 to 63 microns, and in particular from 5 to 40 microns.
  • the spray-dried particles may have a volume average particle size of greater than 10 microns, for example greater than 15 microns. It has been found that spray-drying of the particles can lead to improved properties compared to other drying methods, such as those that involve coagulation.
  • the resulting dried mixture can then be formed into a plastisol, by adding one or more plasticisers.
  • Plasticisers suitable for use with PVC are well known to the skilled person. Typical examples include orthophthalate, terephthalate, adipate, sebacate, succinate, azelate, cyclohexanoate, alkyl sulfonate, phosphate, acetate, butyrate, valerate, benzoate, dibenzoate, trimellitate and vegetable oil-based plasticisers.
  • the plasticiser is selected from esters of di- or tri-carboxylic acids, which can be aliphatic, aromatic or alkylaromatic carboxylic acids.
  • esters can be represented by the formula A[-C(0)OZ] x , where x is 2 or 3.
  • A can be selected from the following groups:
  • a C 2-20 saturated aliphatic group e.g. C 2-14 group
  • one or more e.g. from 1 to 3
  • substituents selected from hydroxyl, Ci- 6 alkoxy, or a phenyl group where the phenyl group is optionally substituted with one or more (e.g. from 1 to 4) C 1-4 alkyl groups;
  • a groups of type (i) are orthophthalate, terephthalate and trimellitate.
  • a groups of type (ii) are adipate, succinate, sebacate, azelate, cyclohexane di carboxyl ate, citrate,
  • Each Z can independently be selected from the following groups;
  • a C 2-20 saturated aliphatic group e.g. C 2-14 group
  • one or more e.g. from 1 to 3
  • substituents selected from hydroxyl, Ci- 6 alkoxy, or a phenyl group where the phenyl group is optionally substituted with one or more (e.g. from 1 to 4) C 1-4 alkyl groups;
  • an ether or polyether group comprising from 2 to 20 (e.g. from 2 to 14) carbon atoms and one or more than one (e.g. from 1 to 6) ether links;
  • Each Z can be the same or different.
  • Z groups of type (i) include methyl, ethyl, butyl, isobutyl, cyclohexyl, octyl,
  • Z groups of type (ii) include 2-butoxyethyl, 2-butoxyethoxyethyl and bis(2- butoxy-ethoxy) ethyl.
  • plasticizers include di(methyl) phthalate (DMP), di(ethyl) phthalate (DEP), di(n-propyl) phthalate, di(butyl) phthalate (DBP), di(isobutyl) phthalate (DIBP), di(n-pentyl) phthalate (DNPP), di(n-hexyl) phthalate (DNHP), di(isohexyl) phthalate (DHP), di(cyclohexyl) phthalate (DCHP), di(isoheptyl) phthalate (DIHP), di(n- octyl) phthalate (DNOP), di(isooctyl) phthalate (DIOP), di(2-ethylhexyl) phthalate (DEHP
  • the plasticisers are selected from esters between monocarboxylic acids with alcohols or other moieties having two or more hydroxyl groups, e.g. from 2 to 6 or from 2 to 4 hydroxyl groups, and can be represented by the formula [AC(0)0-] y Z- (OH)z-y, where z is at least 2 (for example in the range of from 2 to 6 or from 2 to 4), and y is in the range of from 1 to z.
  • Each A can be independently selected from:
  • a C 2-20 saturated aliphatic group e.g. C 2-14 group
  • one or more e.g. from 1 to 3
  • substituents selected from hydroxyl, Ci- 6 alkoxy, or a phenyl group where the phenyl group is optionally substituted with one or more (e.g. from 1 to 4) C 1-4 alkyl groups.
  • Each A can be the same or different.
  • Examples of A groups of type (i) include benzoate.
  • Examples of type (ii) include acetate, butyrate and valerate.
  • Each Z can independently be selected from the following groups;
  • a C2-20 saturated aliphatic group e.g. C2-14 group
  • one or more e.g. from 1 to 3
  • substituents selected from hydroxyl, Ci- 6 alkoxy, or a phenyl group where the phenyl group is optionally substituted with one or more (e.g. from 1 to 4) C1-4 alkyl groups;
  • an ether or polyether group comprising from 2 to 20 (e.g. from 2 to 14) carbon atoms and one or more than one (e.g. from 1 to 6) ether links, optionally with one or more -OH substituents;
  • Z groups of type (i) include aliphatic alkyl groups derived from ethylene glycol (i.e. a CH 2 CH 2 group), propylene glycol (i.e. a CH 3 CHCH 2 group), pentaerythritol (i.e. a C[CH CH2] 4 group), 2, 2, 4-trimethyl- 1, 3 -pentanediol (i.e. a
  • Z groups of type (ii) include aliphatic groups derived from di, tri or tetraethyl ene glycol (i.e. a CH2CH2-O-CH2CH2, CH2CH2-O-CH2CH2-O-CH2CH2 or CH2CH2-O-CH2CH2-O-CH2CH2-O-CH2CH2 groups), aliphatic groups derived from di, tri or tetrapropylene glycol (e.g.
  • C represents a carbon atom bound to the O- of an [AC(0)0-] group or an -OH group.
  • plasticisers include diethylene glycol dibenzoate, dipropyleneglycol dibenzoate, triethyleneglycol dibenzoate, gly eery ltri acetate, 2, 2,4- trim ethyl -1,3 -pentanedi ol -di (i sobuty rate), pentaerythritol tetraval erate .
  • the plasticisers can also be selected from monoesters of formula AC(0)0Z, where A is a benzene ring, optionally substituted by one or more (e.g. from 1 to 4) Ci-4 alkyl groups, and Z is selected from a Cs-2o saturated aliphatic group (e.g.
  • Cs-i4 group optionally substituted with one or more (e.g. from 1 to 3) substituents selected from hydroxyl, Ci- 6 alkoxy, or a phenyl group where the phenyl group is optionally substituted with one or more (e.g. from 1 to 4) Ci-4 alkyl groups.
  • plasticisers examples include isononyl benzoate (INB) and isodecyl benzoate (IDB).
  • the plasticisers can also be selected from phosphate esters of general formula P(0)(0Z) 3 , or from alkyl sulfonic acid esters of formula T-S(0) 2 0Z, where each Z can independently be selected from
  • a C2-20 saturated aliphatic group e.g. C2-14 group
  • one or more e.g. from 1 to 3
  • substituents selected from hydroxyl, Ci- 6 alkoxy, or a phenyl group where the phenyl group is optionally substituted with one or more (e.g. from 1 to 4) C1-4 alkyl groups;
  • the group T is typically a C10-C21 alkyl group, and Z is not H.
  • plasticisers in this category include tri(phenyl) phosphate (TPP), and 2- ethylhexyl di(phenyl) phosphate (EHDP), tri(2-ethylhexyl) phosphate and alkyl sulfonic acid phenyl ester (ASE), where the alkyl group can be Cio-21 or C 14-16 alkyl.
  • plasticiser examples include polymeric plasticisers formed from reaction of diacids with diols.
  • the diacids are typically C 4 -C 18 alkyl diacids, for example C 4-8 diacids such as hexanedioic acid.
  • the diols are typically C 2 -C 10 diols, for example ethylene glycol or propylene glycol.
  • the polymer chains can be terminated by C2-12 carboxylate groups. Examples of these types of polymeric plasticisers include polymers of hexanedioc acid with propylene glycol, and their esters with acetate, octanoate and isononylate.
  • Examples of vegetable oil plasticisers include epoxidised, hydrogenated and esterified vegetable oils. Examples are described in EiS 2002/013396.
  • blowing agent is also included in the plastisol.
  • These are typically compounds that are solid or liquid at room temperature, but either gasify, or decompose to release a gas, when exposed to heat. Blowing agents are well known to those skilled in the field of PVC processing.
  • Liquid blowing agents that form foams through evaporation include organic compounds, typically alkanes and haloalkanes, that boil above 25°C (at atmospheric pressure), and below 200°C. Examples include C5-C12 linear, branched and cyclic alkanes, or C2-C10 linear, branched and cyclic alkanes substituted with one or more halides selected from Cl and F. They also include dialkyl ethers, typically comprising C2 to C5 alkyl groups, where the alkyl groups can be linear, branched or cyclic. An example of using such blowing agents in PVC is described in US6225365.
  • Blowing agents that form foams through decomposition are typically those which release nitrogen (e.g. compounds comprising an azo group), or carbon dioxide (e.g. carbonate- containing compounds). Specific examples of such blowing agents include
  • ADC azodicarbonamide
  • OBSH oxybissulphonylhydrazide
  • sodium bicarbonate sodium bicarbonate
  • the resulting foam typically has a density in the range of from 200 to 500 kg m 3 .
  • the density is in the range of from 200 to 450 kg m 3 , for example in the range of from 250 to 360 kg m 3 .
  • the density of the foams can be measured using ISO R 1183 : 1987 Part 1.
  • An E-PVC latex (PevikonTM PI 5) was dried using a NiroTM rotary disk dryer, with an outlet air temperature of 68°C.
  • the dried material was then formed into a plastisol by combining 100 parts by weight with 50 parts by weight PalatinolTM N di-isononyl phthalate (DINP) and 3 parts by weight GenitronTM SCE azodicarbonamide blowing agent, and mixing using a HobartTM planetary mixer.
  • DINP PalatinolTM N di-isononyl phthalate
  • GenitronTM SCE azodicarbonamide blowing agent was then formed into a plastisol by combining 100 parts by weight with 50 parts by weight PalatinolTM N di-isononyl phthalate (DINP) and 3 parts by weight GenitronTM SCE azodicarbonamide blowing agent, and mixing using a HobartTM planetary mixer.
  • the plastisol was then cast into a 100 p -thick sheet, and heated to a temperature of 205°C for 60 seconds in order to produce a foam.
  • Example 1 The procedure of Example 1 was followed, except that the initial E-PVC latex was mixed with 1 phr (part per hundred resin) LevasilTM CS15-150 colloidal silica, based on dry weight, before the mixture was dried.
  • LevasilTM CS15-150 is an aqueous colloidal silica comprising 15wt% silica, and is made by particle growth from water glass-derived silicic acid.
  • the surface area of the colloidal silica particles is 500 m 2 g 1 (particle size 5 nm based on Equation 1).
  • Example 3
  • Example 2 The procedure of Example 2 was followed, except that lphr (on a dry basis) of LevasilTM CS30-236 was added to the E-PVC latex.
  • LevasilTM CS30-236 is an aqueous colloidal silica comprising 30wt% silica, and is made by particle growth from water glass-derived silicic acid.
  • the surface area of the colloidal silica particles is 360 m 2 g 1 (particle size 7 nm based on Equation 1).
  • Example 2 The procedure of Example 2 was followed, except that lphr of a modified colloidal silica was used.
  • the modified colloidal silica was prepared by treating LevasilTM C S30-236 with (3- glycidyloxypropyl)triethoxysilane and n-propyl triethoxysilane according to the general procedure described on page 8 of WO 2004/035473, which involved adding the appropriate amount of (3 -glycidyloxypropyl)tri ethoxy silane and n-propyl triethoxysilane (in a 60:40 molar ratio) to the unmodified colloidal silica, and stirring at room temperature for 2 hours.
  • the lphr loading of the modified colloidal silica is based on the weight of“bare” silica (expressed as SiCE), i.e. without silane, to the weight of PVC resin, on a dry basis.
  • the total amount of organosilane reagents was chosen so as to provide a degree of modification (DM) on the silica particle surface of 1.4 nm 2 .
  • Example 4 The procedure of Example 4 was followed, except that the modified colloidal silica used was prepared by modification of LevasilTM CS15-150 with (3- glycidyloxypropyl)triethoxysilane and n-propyltriethoxysilane in a 60:40 molar ratio.
  • the total amount of organosilane reagents was chosen so as to provide a degree of modification (DM) on the silica particle surface of 1.4 nm 2 .
  • Example 2 The procedure of Example 2 was followed, except that a non-colloidal solid form of silica (SidistarTM T120U) was added to the E-PVC latex instead of a colloidal silica.
  • a non-colloidal solid form of silica SidistarTM T120U
  • SidistarTM T120U has a surface area of 18-25 m 2 g _1 , and a median particle size of 150 nm.
  • silicas other than colloidal silicas can have similar primary particle sizes to colloidal silicas.
  • colloidal silicas used in the present Examples comprise a dispersion of the primary particles in an aqueous medium prepared by particle growth, solids forms of silicas tend to be formed of agglomerates of primary silica particles.
  • Example 2 the plastisol formed was cast into a 100 p -thick sheet, and heated to a temperature of 205°C for 60 seconds in order to produce a foam.
  • Example 7 The procedure of Example 7 was followed, except that 1 phr of colloidal silica LevasilTM CS50-28 was added to the E-PVC latex before the mixture was dried.
  • LevasilTM CS50-28 is an aqueous colloidal silica with a silica content of 50wt%. It is made by particle growth from water glass-derived silicic acid. The surface area of the colloidal silica particles is 80 m 2 g 1 (particle size 34 nm based on Equation 1).
  • Example 9
  • Example 8 The procedure of Example 8 was followed, except that 3 phr of colloidal silica LevasilTM CS50-28 was added to the E-PVC latex.
  • Example 7 The procedure of Example 7 was followed, except that 1 phr of colloidal silica LevasilTM CS40-217 was added to the E-PVC latex before the mixture was dried.
  • LevasilTM CS-40-217 is an aqueous colloidal silica with a silica content of 40 wt%. It is made by particle growth from water glass-derived silicic acid. The surface area of the colloidal silica particles is 170 m 2 g 1 (particle size 16 nm based on Equation 1).
  • Example 10 The procedure of Example 10 was followed, except that 3 phr of colloidal silica LevasilTM CS40-217 was added to the E-PVC latex.
  • Example 7 The procedure of Example 7 was followed, except that 1 phr of fumed silica SidistarTM T120U was added to the E-PVC latex before the mixture was dried.
  • Example 12 The procedure of Example 12 was followed, except that 3 phr of fumed silica SidistarTM T120U was added to the E-PVC latex. Examples 14 to 20
  • Examples 14 to 20 are comparative examples.
  • silica-containing plastisols show higher viscosity, although these differences diminish at higher shear rates. This demonstrates that the presence of silica or colloidal silica in the plastisol does not have a significant negative impact on the rheology of the PVC, and hence such plastisols should still be suitable for use in foam production.
  • the density of foams formed from the 100 pm plastisol films of Examples 1 to 6 are shown in Figure 2.
  • the colloidal silica-modified PVC foams are significantly less dense that the silica-free foam.
  • modified and unmodified colloidal silica produce lower density foams compared to the non-colloidal silica-containing foams.
  • Figure 3 shows the foam density data for Examples 7 to 13.
  • colloidal silica and modified colloidal silica provide foams of lower density compared to silica-free materials, and materials comprising alternative sources of silica, e.g. fumed silica.
  • the expansion of the colloidal silica-containing foams was comparable to or better than the silica-free reference samples or the samples prepared using alternative silica sources, e.g. fumed silica.
  • the modified and unmodified colloidal silica-containing samples all showed superior performance, i.e. reduced yellowing, compared to the silica-free samples. Further, they showed comparable or improved results compared to the samples made using non-colloidal silica, e.g. fumed silica.
  • Figures 9A-G are photographs of the bubble structure of PVC foams made from the 400 pm thick plastisol films of Examples 14 to 20 (corresponding to examples 7-13
  • Colloidal silica offers advantages in the production of PVC foams compared to colloidal silica-free materials, or materials prepared using alternative sources of silica, such as fumed silica.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Emergency Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un procédé de production d'une forme PVC, comprenant le mélange d'une dispersion de PVC avec de la silice colloïdale, le séchage du mélange de PVC et de silice colloïdale pour former un mélange de PVC-silice colloïdale sec, la formation d'un plastisol par ajout d'un plastifiant et d'un agent de soufflage au mélange de PVC-silice colloïdale sec, et le chauffage du plastisol à une température suffisante pour provoquer la formation d'une mousse. L'invention concerne également une mousse de PVC comprenant des particules de silice dérivées de silice colloïdale, et qui peut être fabriquée à l'aide du procédé ci-dessus. L'invention concerne en outre l'utilisation de silice colloïdale dans la fabrication de mousse de PVC, en particulier pour réduire sa densité.
PCT/EP2020/063062 2019-05-14 2020-05-11 Mousses de pvc WO2020229416A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP19174523.1 2019-05-14
EP19174523 2019-05-14

Publications (1)

Publication Number Publication Date
WO2020229416A1 true WO2020229416A1 (fr) 2020-11-19

Family

ID=66554200

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2020/063062 WO2020229416A1 (fr) 2019-05-14 2020-05-11 Mousses de pvc

Country Status (1)

Country Link
WO (1) WO2020229416A1 (fr)

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB923458A (en) * 1960-05-24 1963-04-10 Lonza Electric & Chem Works Expanded materials based on vinyl chloride polymers and copolymers
CA891538A (en) * 1972-01-25 M. Pikarsky Jacob Plastisol composition
US3708441A (en) 1970-10-19 1973-01-02 Dow Corning Process for making pvc foams
GB1360392A (en) * 1970-07-31 1974-07-17 Fisons Ltd Foamable thermoplastic compositions
US4029612A (en) * 1970-07-31 1977-06-14 Fisons Limited Silica containing blowing agent compositions as plate-out preventives in foamed plastics processes
US4927749A (en) 1986-04-09 1990-05-22 Jeanette Simpson Reagent for cell separation
US6225365B1 (en) 2000-04-19 2001-05-01 Atofina Chemicals, Inc. PVC foam
US20020013396A1 (en) 2000-06-20 2002-01-31 Battelle Memorial Institute Plasticizers derived from vegetable oils
WO2004035474A1 (fr) 2002-10-14 2004-04-29 Akzo Nobel N.V. Dispersion aqueuse de silice
EP2428531A1 (fr) 2010-09-10 2012-03-14 Ineos Norge Holdings AS Composition de polymère et son procédé de fabrication
WO2015007522A1 (fr) 2013-07-15 2015-01-22 Ineos Norge Holdings As Composite et procédés de production
WO2016050603A1 (fr) 2014-10-01 2016-04-07 Sika Technology Ag Procédé de fabrication et composition pour protections de blindage de canalisation en pvc-p expansé
WO2018011182A1 (fr) * 2016-07-14 2018-01-18 Akzo Nobel Chemicals International B.V. Microsphères thermoplastiques expansibles thermiquement et leur procédé de préparation

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA891538A (en) * 1972-01-25 M. Pikarsky Jacob Plastisol composition
GB923458A (en) * 1960-05-24 1963-04-10 Lonza Electric & Chem Works Expanded materials based on vinyl chloride polymers and copolymers
GB1360392A (en) * 1970-07-31 1974-07-17 Fisons Ltd Foamable thermoplastic compositions
US4029612A (en) * 1970-07-31 1977-06-14 Fisons Limited Silica containing blowing agent compositions as plate-out preventives in foamed plastics processes
US3708441A (en) 1970-10-19 1973-01-02 Dow Corning Process for making pvc foams
US4927749A (en) 1986-04-09 1990-05-22 Jeanette Simpson Reagent for cell separation
US6225365B1 (en) 2000-04-19 2001-05-01 Atofina Chemicals, Inc. PVC foam
US20020013396A1 (en) 2000-06-20 2002-01-31 Battelle Memorial Institute Plasticizers derived from vegetable oils
WO2004035474A1 (fr) 2002-10-14 2004-04-29 Akzo Nobel N.V. Dispersion aqueuse de silice
WO2004035473A1 (fr) 2002-10-14 2004-04-29 Akzo Nobel N.V. Dispersion de silice colloidale
EP2428531A1 (fr) 2010-09-10 2012-03-14 Ineos Norge Holdings AS Composition de polymère et son procédé de fabrication
WO2015007522A1 (fr) 2013-07-15 2015-01-22 Ineos Norge Holdings As Composite et procédés de production
WO2016050603A1 (fr) 2014-10-01 2016-04-07 Sika Technology Ag Procédé de fabrication et composition pour protections de blindage de canalisation en pvc-p expansé
WO2018011182A1 (fr) * 2016-07-14 2018-01-18 Akzo Nobel Chemicals International B.V. Microsphères thermoplastiques expansibles thermiquement et leur procédé de préparation

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
GREENWOODGEVERT, PIGMENT AND RESIN TECHNOLOGY, vol. 40, no. 5, 2011, pages 275 - 284
ILERDALTON, J. PHYS. CHEM., vol. 60, 1956, pages 955 - 957
ILERK. RALPH: "The Chemistry of Silica", 1979, JOHN WILEY & SONS, pages: 465
SEARS, ANAL. CHEM., vol. 28, no. 12, 1956, pages 1981 - 1983

Similar Documents

Publication Publication Date Title
JP5602996B2 (ja) 粉末状のシリカコンポジット粒子及びその製造方法、シリカコンポジット粒子分散液、並びに樹脂組成物
US4344800A (en) Method for producing hydrophobic reinforcing silica fillers and fillers obtained thereby
US9388314B2 (en) Surface modified silicon dioxide particles
US11214492B2 (en) Silica particles
JP5275562B2 (ja) 粉末状のシリカコンポジット粒子及びその製造方法、シリカコンポジット粒子分散液、並びに樹脂組成物
JP6236676B2 (ja) フッ素含有ナノコンポジット粒子及びその製造方法、並びにこれを含むコーティング剤、油水分離膜、樹脂組成物
JP2015522691A (ja) Ｐｖｃ難燃性組成物
WO2020229406A1 (fr) Composition comprenant du chlorure de polyvinyle (pvc) et de la silice colloïdale modifiée par organosilane et procédé de préparation associé
US20170342186A1 (en) Impact Strength Modifier for Chlorine-Containing Resin, Chlorine-Containing Resin Composition and Molded Body of Chlorine-Containing Resin Composition
JP2010077383A (ja) シロキサン結合を主骨格とするナノコンポジット粉末状粒子及びその製造方法、シロキサン結合を主骨格とするナノコンポジット粉末状粒子分散液、並びに樹脂組成物
WO2020229416A1 (fr) Mousses de pvc
JP2015030827A (ja) ポリテトラフルオロエチレンパウダー組成物、これからなるドリップ防止剤及びこれを含む樹脂組成物
US20160017198A1 (en) Fluorine-containing nano-silica composite particles and method for producing the same
JP5826679B2 (ja) パーフルオロカーボンスルホン酸ポリマー含有ナノコンポジット粒子の製造方法
JP2010235943A (ja) シロキサン結合を主骨格とするナノコンポジット粉末状粒子及びその製造方法、シロキサン結合を主骨格とするナノコンポジット粉末状粒子分散液、並びに樹脂組成物
JP2005306905A (ja) 塩化ビニル系プラスチゾル組成物及び発泡成形体
JP2021169568A (ja) ペースト加工用塩化ビニル系樹脂組成物及びその用途
JP7149535B2 (ja) 塩化ビニル－酢酸ビニル共重合体樹脂組成物
DK2336236T3 (en) Chlorinated resin composition with suppressed foam formation defect
JP2006306963A (ja) 塩化ビニル系ペースト樹脂
JP2010209300A (ja) フラーレンを含有するナノコンポジット粉末状粒子及びその製造方法、ナノコンポジット粉末状粒子分散液、並びに樹脂組成物
JP6451922B2 (ja) 水性被覆材および塗装物
JP2014167050A (ja) カーボンナノチューブ組成物、並びにこれを用いた樹脂組成物及び成形体
CN107602767A (zh) 核壳粒子，其制造方法及应用
JP5272356B2 (ja) ペースト加工用塩化ビニル系樹脂及びその製造方法、並びにその用途

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20723442

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20723442

Country of ref document: EP

Kind code of ref document: A1